Compounds derived from polyanhydride resins with film-forming, UV-absorbing, and photostabilizing properties, compositions containing same, and methods of using the same

ABSTRACT

Polymers containing one or more crylene moieties attached to the polymer backbone, sunscreen compositions including a mixture of a photoactive compound and a polymer containing one or more crylene moieties attached to the polymer backbone are described herein. Also disclosed are methods for stabilizing a sunscreen composition and methods of filtering out ultra-violet light from a substrate by the addition of one or more of the foregoing polymers, and methods of waterproofing and forming a film with one or more of the foregoing polymer are described herein.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of application Ser. No.10/786,793 filed Feb. 25, 2004.

BACKGROUND

1. Field of the Technology

The invention relates to polymers, and methods to increase theUV-absorbance, water resistance, and photostability of a variety ofcompositions. More particularly, the invention relates tocyanodiphenylacrylate and/or cyanofluorenylidene acetate compounds andcompositions containing the same, and methods of using them that includea method of protecting a material from ultra-violet radiation, a methodof waterproofing, a method of forming a film, and a method ofphotostabilizing a photounstable compound.

2. Brief Description of Related Technology

It is well known that ultraviolet radiation (light) having a wavelengthfrom about 280 nm or 290 nm to about 320 nm (UV-B) is harmful to humanskin, causing burns that are detrimental to the development of a goodsun tan. UV-A radiation (about 320 nm to about 400 nm), while producingtanning of the skin, also can cause damage, particularly to verylightly-colored or sensitive skin, leading to reduction of skinelasticity and wrinkles. Therefore, a sunscreen composition for use onhuman skin preferably includes both a UV-A and a UV-B filter to preventmost of the sunlight within the full range of about 280 nm or 290 nm toabout 400 nm from damaging human skin.

Ultraviolet radiation from the sun or artificial sources can also causeharm to coatings containing photoactive substances, such as photoactivepigments and dyes, by breaking down chemical bonds in the structure of acomponent such as a polymer, a pigment, or a dye. This photodegradationcan lead to color fading, loss of gloss, and loss of physical andprotective properties of a coating. Photodegradation can take place inseveral steps which include one or more components of a coatingabsorbing UV radiation. The absorbed radiation can excite the absorbingmolecules and raise them to a higher energy level, which can be veryreactive. If the molecule cannot be relaxed, bond cleavage and theformation of free radicals will occur. These free radicals can attackone or more color molecules and/or a polymer backbone and form more freeradicals.

UV-A and UV-B filters can also be used to absorb UV radiation to protecta pigmented coating. The UV-B filters that are most widely used in theU.S. in commercial sunscreen compositions are paramethoxycinnamic acidesters, such as 2-ethylhexyl paramethoxycinnamate, commonly referred toas octyl methoxycinnamate or PARSOL MCX; octyl salicylate; andoxybenzone.

The organic UV-A filters most commonly used in commercial sunscreencompositions are the dibenzoylmethane derivatives, particularly4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane (also calledavobenzone, sold under the brand name PARSOL 1789). Otherdibenzoylmethane derivatives described as UV-A filters are disclosed inU.S. Pat. Nos. 4,489,057, 4,387,089 and 4,562,067, the disclosures ofwhich are hereby incorporated herein by reference. It is also well knownthat the above described UV-A filters, particularly the dibenzoylmethanederivatives, can suffer from rapid photochemical degradation, when usedalone or when combined with the above-described most commercially usedUV-B filters.

Typically, the above-described UV-B filters are combined with the abovedescribed UV-A filters in a solution with other lipophilic or oilyingredients. This solution of oily ingredients, known to formulators ofcosmetic products including sunscreens as the “oil phase,” is typically,but not necessarily, dispersed with the help of emulsifiers andstabilizers into an aqueous solution composed primarily of water, tomake an emulsion which becomes a final cream or lotion form of asunscreen composition.

The performance of a photoactive compound or a combination ofphotoactive compounds in a sunscreen composition has been extremelydifficult to predict based on the levels of photoactive compounds in theformulation, particularly when the formulation includes one or morephotoactive compounds that suffer from relatively rapidphotodegradation, such as avobenzone. Because of this, each formulationhas required expensive laboratory testing to determine the UVabsorbance, as a function of time (quantity) of exposure of theformulation to UV radiation. Moreover, a particularly difficult problemis presented when one photoactive compound in a sunscreen compositionacts to increase the rate of photodegradation of another photoactivecompound in the composition. This can be accomplished in a number orways, including a bimolecular reaction between two photoactive compoundsand a lowering of the threshold energy needed to raise a photoactivecompound to its excited state. For example, when avobenzone is combinedwith octyl methoxycinnamate a bimolecular pathway leads to the rapidphotodegradation of both the dibenzoylmethane derivative and the octylmethoxycinnamate.

Methods and compositions for stabilizing photoactive compounds, such asdibenzoylmethane derivatives, with the use of octocrylene and fluoreneare described in the commonly-assigned U.S. Pat. Nos. 5,993,789,6,113,931, 6,126,925, and 6,284,916, the disclosures of which are herebyincorporated herein by reference. Other methods of stabilizing adibenzoylmethane derivative include the addition of anα-cyano-β,β-diphenylacrylate compound to a sunscreen compositionincluding a dibenzoylmethane derivative. See, Deflandre et al, U.S. Pat.No. 5,576,354 and Gonzenbach et al., U.S. Pat. No. 6,033,649.

SUMMARY

One aspect of the compounds, compositions, and methods described hereinis to provide a polymeric compound having a crylene moiety((2E)-2-cyano-3,3-diphenylprop-2-enoic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods describedherein is to provide a sunscreen composition that includes aUV-absorbing polymeric compound having a crylene moiety((2E)-2-cyano-3,3-diphenylprop-2-enoic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods describedherein is to provide a method of reducing or eliminating an amount ofultra-violet light that contacts a substrate by disposing between thesource of ultra-violet light and the substrate, or applying to thesubstrate a polymeric compound having a crylene moiety((2E)-2-cyano-3,3-diphenylprop-2-enoic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods describedherein is to provide a method of waterproofing a substrate surface byapplying thereto a polymeric compound having a crylene moiety((2E)-2-cyano-3,3-diphenylprop-2-enoic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods describedherein is to provide a method of protecting a photodegradable materialagainst photodegradation by applying thereto a polymeric compound havinga crylene moiety ((2E)-2-cyano-3,3-diphenylprop-2-enoic acid) attachedto the polymer backbone.

Another aspect of the compounds, compositions, and methods describedherein is to provide a method of forming a UV-absorbing film on asubstrate surface by applying thereto film or coating containing apolymeric compound having a crylene moiety((2E)-2-cyano-3,3-diphenylprop-2-enoic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods describedherein is to provide a method for photostabilizing a sunscreencomposition including a photoactive compound by the addition of aphotostabilizing effective amount of a polymeric compound having acrylene moiety ((2E)-2-cyano-3,3-diphenylprop-2-enoic acid) attached tothe polymer backbone.

Further aspects and advantages of the invention will be apparent tothose skilled in the art from a review of the following detaileddescription, taken in conjunction with the appended claims. While thecompounds, compositions, and methods are susceptible of embodiments invarious forms, the description hereinafter includes specific embodimentsof the invention with the understanding that the disclosure isillustrative, and is not intended to limit the inventions to thespecific embodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the absorbance of a sunscreen composition thatincludes 2% Octadecene/Crylene maleate copolymer as the onlyUV-absorbing compound, from a wavelength of 280 nm to 400 nm.

FIG. 2 is a graph of the absorbance of a sunscreens composition thatincludes 2% Octadecene/Crylene maleate copolymer as the onlyUV-absorbing compound, a sunscreen composition (with UV-absorbingcompounds) that does not include Octadecene/Crylene maleate copolymer,and a sunscreen composition including 2% of the Octadecene/Crylenemaleate copolymer and other UV-absorbing compounds, from a wavelength of280 nm to 400 nm.

FIG. 3 is a graph of the original absorbance of a sunscreen compositionthat does not include Octadecene/Crylene maleate copolymer from awavelength of 280 nm to 400 nm and after the composition has beenexposed to 35 MED.

FIG. 4 is a graph of the original absorbance of a sunscreen compositionthat includes 2% of the Octadecene/Crylene maleate copolymer from awavelength of 280 nm to 400 nm and after the composition has beenexposed to 35 MED.

FIG. 5 is a graph of the original absorbance of a sunscreen compositionincluding 2% Octadecene/Crylene maleate copolymer, and a sunscreencomposition not including Octadecene/Crylene maleate copolymer, whereinthe absorbance is measured from a wavelength of 280 nm to 400 nm andafter the compositions have been exposed to 35 MED.

FIG. 6 is a graph of the absorbance of a sunscreen composition that doesnot include Octadecene/Crylene maleate copolymer, from a wavelength of280 nm to 400 nm.

FIG. 7 is a graph of the absorbance of a sunscreen composition thatincludes 2% Octadecene/Crylene maleate copolymer, from a wavelength of280 nm to 400 mm.

FIG. 8 is a graph of the original absorbance of a sunscreen compositionthat did not include the Octadecene/Crylene maleate copolymer, measuringthe absorbance from a wavelength of 280 nm to 400 nm, and after thecomposition was immersed in water for 40 minutes.

FIG. 9 is a graph of the original absorbance of a sunscreen compositionthat includes 2% of the Octadecene/Crylene maleate copolymer, measuringthe absorbance from a wavelength of 280 nm to 400 nm, and after thecomposition was immersed in water for 40 minutes.

FIG. 10 is a graph of the original absorbance of a sunscreen compositionthat includes 2% of the Octadecene/Crylene maleate copolymer, and asunscreen composition that did not include the Octadecene/Crylenemaleate copolymer, measuring the absorbance from a wavelength of 280 nmto 400 nm, and after the compositions were immersed in water for 40minutes.

FIG. 11 is a graph of the original absorbance of a sunscreen compositionthat includes 2% of the Crylene/Cetyl Polymer, and a sunscreencomposition that did not include the Crylene/Cetyl Polymer, measuringthe absorbance from a wavelength of 280 nm to 400 nm.

FIG. 12 is a graph of the original absorbance of a sunscreen compositionthat includes 2% of the Crylene/Behenyl Polymer, and a sunscreencomposition that did not include the Crylene/Behenyl Polymer, measuringthe absorbance from a wavelength of 280 nm to 400 nm.

FIG. 13 is a graph of the original absorbance of a sunscreen compositionthat includes 2% of the Crylene/Behenyl Polymer, and a sunscreencomposition that did not include the Crylene/Behenyl Polymer, measuringthe absorbance from a wavelength of 280 nm to 400 nm, and after thecompositions were immersed in water for 40 minutes.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Sunscreen compositions typically include one or more photoactivecompounds that can absorb UV radiation, and often sunscreen compositionsinclude a variety of photoactive compounds to absorb UV-radiation overthe entire UV range (UV-A and UB-B range). Polymers and compositionsthat include photoactive moieties, including crylene((2E)-2-cyano-3,3-diphenylprop-2-enoic acid)) and/or fluorene(2-cyano-2-fluoren-9-ylideneacetic acid), and methods of use of suchpolymers are described herein.

The general structure of a crylene moiety((2E)-2-cyano-3,3-diphenylprop-2-enoic acid) is shown below:

Optionally, each of the aromatic rings on the core crylene moiety can besubstituted with various functional groups. Alpha-cyano-beta,beta-diphenylacrylate compounds, such as Octocrylene(2-ethylhexyl(2Z)-2-cyano-3,3-diphenylprop-2-enoate), are known toquench (accept the excited state energy) of an excited photoactivecompound (see, e.g., the commonly assigned U.S. patent application Ser.Nos. 10/241,388, 10/361,223, and 10/785,271.) Without intending to belimited to any particular mechanism by which anα-cyano-β,β-diphenylacrylate compound is able to quench the excitedstate of photoactive compound, it is theorized that theα-cyano-β,β-diphenylacrylate compound accepts the excited state energyand dissipates the energy kinetically in the form of rapidisomerizations. This process is shown below:

wherein the α-cyano-β,β-diphenylacrylate compound (octocrylene shownabove as structure A), accepts the triplet excited state energy from aphotoactive compound and forms a diradical (shown above as structure A*)at the α and β positions of the acrylate, which converts the double bondinto a single bond and allows for the free rotation of the phenylgroups. This rotation occurs rapidly and efficiently to dissipate anyexcited state energy accepted by the α-cyano-β,β-diphenylacrylatecompound from the photoactive compound. In solution (e.g., a sunscreencomposition), a key limitation on the ability of a compound tophotostabilize another compound is the ability of the two compounds tocome into contact with one another.

The general structure of a fluorene moiety(2-cyano-2-fluoren-9-ylideneacetic acid) is shown below:

Optionally, each of the aromatic rings on the core fluorene moiety canbe substituted with various functional groups.

It has also been discovered that the novel UV-absorbing andphotostabilizing compounds disclosed in the commonly assigned U.S.patent application Ser. Nos. 10/246,434, 10/458,286, and 10/385,833 andU.S. Pat. No. 6,800,274, the disclosures of which are herebyincorporated by reference, may be attached to a polymer molecule toprovide other novel UV-absorbing and photostabilizing polymers. It hasalso been found that the polymer resulting from the attachment to thepolymer backbone of the photostabilizing compounds disclosed in theabove-listed applications would create a polymer that can absorbUV-radiation and photostabilize one or more other photoactive compoundsin a UV-absorbing composition.

In accordance with another important “tether” embodiment of thecompounds, compositions, and methods described herein, it has also beendiscovered that by attaching a tether to the crylene and/or fluorenemoieties and attaching the crylene and/or fluorene moieties to thepolymer backbone via the tether, the crylene and fluorene moieties arethereby spaced from the polymer backbone by attaching a tether (aspacer) so that there is less steric interference, to provide a moreeffective and efficient energy absorption and dissipation of the excitedstate energy via the aromatic ring(s) spinning about the tether(spacer). Suitable tether molecules include diols, diamino compounds, orany compound with two or more functional groups, wherein at least onefunctional group can be covalently attached to the carboxylic acid onthe crylene and/or fluorene moieties (e.g., an alcohol, amine,carboxylic acid, a sulfide), and another functional group that can becovalently bonded to the polymer backbone. Nonlimiting examples ofsuitable tethers include alkyl diols (e.g., 2,2-dimethylpropane-1,3-dioland 3,3-dimethylpentane-1,5-diol), alkyl diamines (e.g.,1,5-diaminopentane), and alkyl amino alcohols (5-amino-1-pentanol).Another advantage to using a tether is the potential to add additionalhydrophobic or hydrophilic groups on the tether to influence thesolubility properties of the resulting polymer.

Any polymers may be used in this “tether” embodiment so long as it iscapable of attachment of a tether molecule to its polymer backbone.Exemplary polymers that are useful include those having on its backbonea free alcohol, carboxylic acid, amine, and/or amido wherein thesefunctional groups can be covalently bonded to a crylene and/or fluorenemoiety, or a suitable tether. Copolymers of an α-olefin and maleicanhydride are particularly suitable for the attachment of a cryleneand/or fluorene moiety. Without intending to be limited to a particularmechanism of attachment, it is theorized that a photoactive compoundsuch as a crylene and/or a fluorene moiety is covalently bonded to acopolymer of an α-olefin and maleic anhydride as shown below forpoly(octadecene-1-co-maleic anhydride):

wherein a and b are each in the range of 2 to 5000; c and d are each inthe range of 0 to 5000; and sum of c plus d is at least 2. A widevariety of photoactive compounds may be added to a polymer backbone thatcontain at least one free acid. Nonlimiting examples of photoactivecompounds that can be used in a polymer described herein includecompounds selected from the group consisting of a compound of formula(XIX), a compound of formula (XX), a compound of formula (XXI), acompound of formula (XXII), a compound of formula (XXIII), a compound offormula (XXIV), and a compound of formula (XXV):

wherein R³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, and R⁴⁵ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ substituted alkyl,C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀substituted alkyne, aryl, substituted aryl, heteroaryl,heterocycloalkyl, substituted heteroaryl and substitutedheterocycloalkyl; X is selected from the group consisting of amino, andoxygen; Y and Z are the same or different and are selected from thegroup consisting of amino, and hydroxyl. These photoactive compounds arederived from known photoactive compounds, and can be prepare fromcommercial available photoactive compounds. For example, the compoundsof formula (XIX) is based on the TINOSORB UV-absorbing product(available from Ciba Specialty Chemicals), and can be prepared from2-(3-Allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (available fromSigma-Aldrich, St. Louis, Mo.) by oxidation of the vinylic double bondand reductive amination with diamines or aminoalcohols, as outlinedbelow:

The compounds of formulae (XX), (XXI), (XXII), (XXIII), and (XXIV) canbe prepared with only minor modifications to commercially availablephotoactive compounds using well known chemistry.

Copolymers that are suitable to be covalently bonded crylene and/orfluorene moiety (with or without a tether) include, but are not limitedto, Poly(alpha olefin-co-maleic anhydride), which can be preparedaccording the procedures set forth in U.S. Pat. Nos. 3,860,700,6,358,892, and Reissue No. 28,475, the disclosures of which are herebyincorporated by reference. Examples of these resins includePoly(octadecene-1-co-maleic anhydride) resin (PA-18 available fromChevron Chemicals Co., San Francisco, Calif.), Poly(styrene-co-maleicanhydride) resin (SMA resins, available from Atofina Chemicals Inc.Philadelphia, Pa.), Poly(ethylene-co-maleic anhydride) resin (EMA,available from Monsanto, St. Louis, Mo.), Poly(isobutene-co-maleicanhydride) resin (ISOBAM available form Kuraray Co. Ltd., Osaka, Japan),and Poly(methylvinylether-co-maleic anhydride) resin (GANTREZ Anavailable from ISP, Wayne, N.J.). Alternatively, a mixture of alphaolefins may be used to form the maleic anhydride copolymer, and therebyprovide a versatile polymer with a number of different properties (e.g.,waterproofing and/or lubricating). Alternately mixtures of alpha olefinscan be used (e.g., Ketjenlube® resins available from Akzo Nobel Co.,Dobbs Ferry, N.Y.). Maleic anhydride polymers made with a mixture ofalpha olefins are described in U.S. Pat. Nos. 3,461,108, 3,560,455,3,560,456, 3,560,457, 3,580,893, 3,706,704, 3,729,450, and 3,729,451,the disclosures of which are hereby incorporated by reference.Preferably, the polymer used according to the invention is a Poly(alphaolefin-co-maleic anhydride) resin; more preferably, the polymer is aPoly(octadecene-1-co-maleic anhydride) resin.

In the preparation of a polymer described herein, the attachment ofphotoactive compounds to the polymer backbone may not proceed to add aphotoactive compound to each and every monomer unit in the startingpolymer. In the preferred polymer Poly(alpha olefin-co-maleic anhydride)resin, the maleic anhydride monomer units (labeled above as SM) mayremain unconverted in the preparation of a polymer described hereinand/or the maleic anhydride ring on some of the monomer units may opento its corresponding diacid monomer unit (labeled above as IM). The lackof reactivity at one or more of the maleic anhydride monomer units maybe desirable in order to control the number of photoactive compoundspresent on the polymer, and to control the properties of the resultingpolymer that may impact on the physical properties of the polymer (e.g.,hydrophobic/hydrophilic interactions, hydrogen bonding). Thus,preferably a polymer described herein includes monomers selected fromthe group consisting of a monomer of formula (V), a monomer of formula(VI), and combinations thereof:

wherein R¹³ and R¹⁴ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; and i and j are each in the range of0 to 200. Preferably, R¹³ and R¹⁴ are the same or different and areselected from the group consisting of C₅-C₂₅ alkyl groups, morepreferably they are the same and are C₁₆ straight chain alkyl groups.

It has been found, quite surprisingly, that the addition of ahydrophobic group on one of the monomer units of the preferred polymer(Poly(alpha olefin-co-maleic anhydride)) improves the film-formingproperties (i.e., spreadability) of the resulting polymer that includephotoactive compounds. Thus, prior to the addition of photoactivecompounds to the polymer, about 10% of the maleic anhydride monomerunits are converted to the diacid under mildly acidic conditions, andone of the acid units are then esterified by commonly known practices.Thus, a polymer described herein preferably includes monomers selectedfrom the group consisting of a monomer of formula (III), a monomer offormula (IV), and combinations thereof:

wherein R⁹ and R¹¹ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R¹⁰ and R¹² are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ substitutedalkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀substituted alkyne; and g and h are each in the range of 0 to 200.Preferably R¹⁰ and R¹² are the same or different and are selected fromthe group consisting of C₁₀-C₃₅ alkyl groups, more preferably C₁₆, C₁₈,and C₂₂ alkyl groups. Depending on the application, it may beadvantageous to use R¹⁰ and R¹² groups that are either polar ornon-polar to influence the solubility of the polymer. Thus, R¹⁰ and R¹²are preferably the same or different and are selected from the groupconsisting of C₃-C₃₀ polyether groups, more preferably2-butoxy-1-ethoxyethane (CH₃CH₂OCH₂CH₂OCH₂CH₂CH₂CH₂—). Preferably R⁹ andR¹¹ are the same or different and are selected from the group consistingof C₅-C₂₅ alkyl groups, more preferably they are the same and are C₁₆straight chain alkyl groups. Preferably, the sum of g and h is at least1.

Polymer backbone molecules of a particular polymer generally exists as amixture of polymer molecules of different chain lengths, wherein thepolymer is described as having a chain length that is an average of thechain lengths of the adjacent polymer molecules. Likewise, the molecularweight of a particular polymer can be determined in a number of ways,including a determination of the Weight Average Molecular Weight(M_(W)), which is the summation of the weights of each different sizedpolymer in a mixture multiplied by the mole fraction of that polymersize in the polymer mixture. Nonlimiting examples of methods ofcalculating a given polymer's Weight Average Molecular Weight includediffusion, sedimentation, flow birefringence, and light scattering.Preferably, a polymer described herein has a Weight Average MolecularWeight is the range of about 20,000 to about 130,000 grams/mole, morepreferable in the range of about 30,000 to about 110,000 grams/mole.

Sunscreen compositions containing one or more photoactive compounds,such as a dibenzoylmethane derivative UV-A filter compound, and apolymer containing one or more of a photoactive compound (e.g., cryleneand/or fluorene moieties) covalently bonded to the polymer backbone arealso described herein. One aspect of the sunscreen compositionsdescribed herein are methods of photostabilizing a sunscreen compositionincluding a dibenzoylmethane derivative, such as4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane (PARSOL® 1789), whereinone or more photoactive compounds present in a sunscreen composition(e.g., avobenzone) are made more photostable by the addition of apolymer that contains one or more photoactive compounds (e.g., cryleneand/or fluorene moieties) covalently bonded to the polymer backbone.Further described herein are methods for filtering out ultra-violetlight from human skin including the step of applying to the skin acosmetically acceptable composition including a polymer that containsone or more photoactive compounds (e.g., crylene and/or fluorenemoieties) covalently bonded to the polymer backbone. Also describedherein is a method of waterproofing a material by forming a film on asurface of a material, wherein the film includes a polymer that containsone or more photoactive compounds (e.g., crylene and/or fluorenemoieties) covalently bonded to the polymer backbone.

A photoactive compound can be considered stable when, for example, after30 MED irradiation the photoactive compound has retained at least about90% of its original absorbance at a wavelength, or over a range ofwavelengths of interest (e.g., the wavelength at which a photoactivecompound has a peak absorbance, such as 350-370 nm for avobenzone).Likewise, a sunscreen composition can include a plurality of photoactivecompounds and a sunscreen composition, as a whole, can be consideredstable when, for example, after 30 MED irradiation the sunscreencomposition has retained at least about 90% of its original absorbanceat one or more wavelengths of interest (e.g., at or near the peakabsorbance wavelength of the primary photoactive compound).

In commonly assigned U.S. patent application Ser. Nos. 10/241,388,10/361,223, and 10/785,271, the disclosures of which are herebyincorporated by reference, it was found that the addition of anα-cyano-β,β-diphenylacrylate compound and a diester or polyester ofnaphthalene dicarboxylic acid were able to stabilize a photounstableUV-absorbing compound, e.g., a dibenzoylmethane derivative, such asPARSOL 1789, in a sunscreen composition. It has surprisingly been foundthat sunscreen compositions containing a combination of (1) a polymerthat contains one or more photoactive compounds (e.g., crylene and/orfluorene moieties) covalently bonded to the polymer backbone, and (2) adiester or polyester of naphthalene dicarboxylic acid can significantlyincrease the photostability of any photounstable component(s) presenttherein (e.g., a dibenzoylmethane derivative). Without intending to belimited to any particular mechanism of achieving this increase inphotostability, it is believed that a diester or polyester ofnaphthalene dicarboxylic acid stabilizes a dibenzoylmethane derivativeby accepting the triplet energy of the dibenzoylmethane derivative oncethe dibenzoylmethane derivative has reached an excited state as a resultof the absorption of ultra-violet light. Once a dibenzoylmethanederivative is excited, it is prone to degrade according to a number ofpathways; however, the degradation of the dibenzoylmethane derivativecan be substantially reduced or prevented by the use of a diester orpolyester of naphthalene dicarboxylic acid to quench (accept) thetriplet excited state energy present in an excited dibenzoylmethanemolecule. Thus, in one pathway of degradation, a dibenzoylmethanederivative is excited to its triplet state and the excited state tripletenergy is released in a bond breaking step, thereby preventing thedibenzoylmethane derivative from further accepting ultra-violetradiation. A diester or polyester of naphthalene dicarboxylic acid maystabilize a dibenzoylmethane derivative by accepting the triplet state(excited state) energy of the excited dibenzoylmethane derivative insuch a way as to convert the excited dibenzoylmethane derivative back toa ground state that is capable of reaccepting (or accepting additional)ultra-violet radiation (energy transfer).

For this process to work continuously, the diester or polyester ofnaphthalene dicarboxylic acid must transfer or convert the energy thatwas accepted from the excited dibenzoylmethane derivative. Withoutintending to be limited to a particular mechanism, it is believed thatwhen a diester or polyester of naphthalene dicarboxylic acid is excitedto its triplet state, it dissipates the triplet excited state energythrough vibrations (e.g., as heat), which in this group of molecules isa relatively slow mode of dissipating energy. It has been found, quitesurprisingly, that by the addition of a polymer that contains one ormore photoactive compounds (e.g., crylene and/or fluorene moieties)covalently bonded to the polymer backbone, such a polymer compounds areable to accept triplet excited state energy from an excited diester orpolyester of naphthalene dicarboxylic acid. Thus, according to onepossible mechanism, the efficiency of the dissipation of the excitedstate energy in an excited diester or polyester of naphthalenedicarboxylic acid is greatly improved by a transfer of energy from anexcited diester or polyester of naphthalene dicarboxylic acid to thepolymer containing one or more photoactive compounds.

Thus, preferably, a composition described herein includes a diester orpolyester of naphthalene dicarboxylic acid selected from the groupconsisting of compounds of formulae (XXX) and (XXXI), and combinationsthereof:

wherein R⁹³ and R⁹⁴ are the same or different and selected from thegroup consisting of C₁-C₂₂ alkyl groups, diols having the structureHO—R⁹¹—OH and polyglycols having the structure HO—R⁹⁰—(—O—R⁹¹—)_(γ)—H;wherein each R⁹⁰ and R⁹¹ is the same or different and selected from thegroup consisting of C₁-C₆ straight or branched chain alkyl groups; andwherein α and γ are each in a range of 1 to 100 and β is in a range of 0to 100.

The method of preparation of particularly useful diesters and polyestersof naphthalene dicarboxylic acid and the use of diesters and polyestersof naphthalene dicarboxylic acid in a sunscreen composition aredescribed in U.S. Pat. Nos. 5,993,789 and 6,284,916, the disclosures ofwhich are hereby incorporated herein by reference. Preferably, aUV-absorbing composition that includes a diester or polyester ofnaphthalene dicarboxylic acid includes a diester of formula (XIV)wherein R⁹³ and R⁹⁴ are 2-ethylhexane and β is 0. Preferably, theWV-absorbing compositions described herein include a diester orpolyester of naphthalene dicarboxylic acid in a range of about 0.1% toabout 15% by weight of the total weight of the composition.

A sunscreen composition can be combined into a cosmetically acceptablecarrier, optionally including emollients, stabilizers, emulsifiers, suchas those known in the art, and combinations thereof. These additives canbe used in preparing an emulsion from an aqueous composition and amixture of a WV filter composition that includes one or more photoactivecompounds and a solvent or a solvent combination that includes one ormore organic solvents. When made, preferably the emulsion is anoil-in-water emulsion, wherein the oil phase is primarily formed from amixture of the filter system and solvent system.

A typical sunscreen composition includes one or more photoactivecompounds, wherein a photoactive compound acts to absorb WV radiationand thereby protect the substrate (e.g., human skin) from the harmfuleffects of WV radiation. The absorption process causes a photoactivecompound to reach an excited state, wherein the excited state ischaracterized by the presence of excited energy (e.g., singlet energy ortriplet energy), as compared to the ground state of the photoactivecompound. Once a photoactive compound reaches an excited state thereexists a number of pathways by which the excited photoactive compoundcan dissipate its excess energy (e.g., triplet energy), however, many ofthose pathways adversely affect the ability of the photoactive compoundto further absorb WV radiation.

It has surprisingly been found that the addition of polymers containingone or more photoactive compounds (e.g., crylene and/or fluorenemoieties) covalently bonded to the polymer backbone increase thephotostability of the sunscreen composition. Without intending to belimited to any particular mechanism by which a such compounds are ableto quench (accept the excited state energy) an excited photoactivecompound, it is believed that, for example the crylene and fluorenemoieties accept the excited state energy and dissipates the energykinetically in the form of rapid isomerizations. An example of thisprocess is shown below wherein the PA-18 polymer(poly(octadecene-1-co-maleic anhydride)) having both crylene andfluorene moieties attached to the polymer backbone:

The polymer accepts the triplet excited state energy from a photoactivecompound and forms a diradical at the α and β positions of the acrylate,which converts the double bond into a single bond and allows for freerotation of the phenyl groups or fluorene group about the single bond.This rotation occurs rapidly and efficiently to dissipate excited stateenergy accepted by a derivative of fluorene.

Commonly-assigned U.S. Pat. Nos. 6,485,713 and 6,537,529, thedisclosures of which are hereby incorporated herein by reference,describe compositions and methods for increasing the photostability ofphotoactive compounds in a sunscreen composition, e.g., by the additionof polar solvents to the oil phase of a composition. It has been found,quite surprisingly, that by increasing the polarity of the oil phase ofa sunscreen composition including a polymer that contains one or morephotoactive compounds (e.g., crylene and/or fluorene moieties)covalently bonded to the polymer backbone, the stability of thesunscreen composition is increased. Thus, in a sunscreen describedherein, preferably, one or more of a highly polar solvent is present inthe oil-phase of the composition. Preferably, a sufficient amount of apolar solvent is present in a sunscreen composition to raise thedielectric constant of the oil-phase of the composition to a dielectricconstant of at least about 7, preferably at least about 8.

A photoactive compound is one that responds to light photoelectrically.In the compositions described herein, a photoactive compound is one thatresponds to UV radiation photoelectrically. For example, photoactivecompounds that respond to UV radiation photoelectrically by rapidphotodegradation can benefit highly from the compositions and methodsdescribed herein, even though the benefits of the compositions andmethods described herein are not limited to such compounds.Photostability is a potential problem with all UV filters because theyare deliberately selected as UV-absorbing molecules. In otherapplications, a photoactive compound may be a pigment or a dye (e.g., ahydrophobic dye).

UV filters include compounds selected from the following categories(with specific examples) including: p-aminobenzoic acid, its salts andits derivatives (ethyl, isobutyl, glyceryl esters;p-dimethylaminobenzoic acid); anthranilates (o-aminobenzoates; methyl,menthyl, phenyl, benzyl, phenylethyl, linalyl, terpinyl, andcyclohexenyl esters); salicylates (octyl, amyl, phenyl, benzyl, menthyl(homosalate), glyceryl, and dipropyleneglycol esters); cinnamic acidderivatives (menthyl and benzyl esters, alpha-phenyl cinnamonitrile;butyl cinnamoyl pyruvate); dihydroxycinnamic acid derivatives(umbelliferone, methylumbelliferone, methylaceto-umbelliferone); camphorderivatives (3-benzylidene, 4-methylbenzylidene, polyacrylamidomethylbenzylidene, benzalkonium methosulfate, benzylidene camphor sulfonicacid, and terephthalylidene dicamphor sulfonic acid); trihydroxycinnamicacid derivatives (esculetin, methylesculetin, daphnetin, and theglucosides, esculin and daphnin); hydrocarbons (diphenylbutadiene,stilbene); dibenzalacetone; benzalacetophenone; naphtholsulfonates(sodium salts of 2-naphthol-3,6-disulfonic and of2-naphthol-6,8-disulfonic acids); dihydroxy-naphthoic acid and itssalts; o- and p-hydroxydiphenyldisulfonates; coumarin derivatives(7-hydroxy, 7-methyl, 3-phenyl); diazoles (2-acetyl-3-bromoindazole,phenyl benzoxazole, methyl naphthoxazole, various aryl benzothiazoles);quinine salts (bisulfate, sulfate, chloride, oleate, and tannate);quinoline derivatives (8-hydroxyquinoline salts, 2-phenylquinoline);hydroxy- or methoxy-substituted benzophenones; uric acid derivatives;vilouric acid derivatives; tannic acid and its derivatives;hydroquinone; and benzophenones (oxybenzone, sulisobenzone,dioxybenzone, benzoresorcinol, 2,2′,4,4′-tetrahydroxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxybenzophenone, octabenzone,4-isopropyldibenzoylmethane, butylmethoxydibenzoylmethane, etocrylene,and 4-isopropyl-dibenzoylmethane).

Particularly useful are: 2-ethylhexyl p-methoxycinnamate, 4,4′-t-butylmethoxydibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyldimethylp-aminobenzoic acid, digalloyltrioleate,2,2-dihydroxy-4-methoxybenzophenone, ethyl4-[bis(hydroxypropyl)]aminobenzoate,2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexylsalicylate,glycerol p-aminobenzoate, 3,3,5-trimethylcyclohexylsalicylate,methylanthranilate, p-dimethylaminobenzoic acid or aminobenzoate,2-ethylhexyl p-dimethylaminobenzoate, 2-phenylbenzimidazole-5-sulfonicacid, 2-(p-dimethylaminophenyl-5-sulfoniobenzoxazoic acid, andcombinations thereof.

For a product marketed in the United States, preferredcosmetically-acceptable photoactive compounds and concentrations(reported as a percentage by weight of the total cosmetic sunscreencomposition) include: aminobenzoic acid (also called para-aminobenzoicacid and PABA; 15% or less), avobenzone (also called butyl methoxydibenzoylmethane; 3% or less), cinoxate (also called 2-ethoxyethylp-methoxycinnamate; 3% or less), dioxybenzone (also calledbenzophenone-8; 3% or less), homosalate (15% or less), menthylanthranilate (also called menthyl 2-aminobenzoate; 5% or less),octocrylene (also called 2-ethylhexyl-2-cyano-3,3 diphenylacrylate; 10%or less), octyl methoxycinnamate (7.5% or less), octyl salicylate (alsocalled 2-ethylhexyl salicylate; 5% or less), oxybenzone (also calledbenzophenone-3; 6% or less), padimate O (also called octyl dimethylPABA; 8% or less), phenylbenzimidazole sulfonic acid (water soluble; 4%or less), sulisobenzone (also called benzophenone-4; 10% or less),titanium dioxide (25% or less), trolamine salicylate (also calledtriethanolamine salicylate; 12% or less), and zinc oxide (25% or less).

Other preferred cosmetically-acceptable photoactive compounds andpreferred concentrations (percent by weight of the total cosmeticsunscreen composition) include diethanolamine methoxycinnamate (10% orless), ethyl-[bis(hydroxypropyl)]aminobenzoate (5% or less), glycerylaminobenzoate (3% or less), 4-isopropyl dibenzoylmethane (5% or less),4-methylbenzylidene camphor (6% or less), terephthalylidene dicamphorsulfonic acid (10% or less), and sulisobenzone (also calledbenzophenone-4, 10% or less).

For a product marketed in the European Union, preferredcosmetically-acceptable photoactive compounds and preferredconcentrations (reported as a percentage by weight of the total cosmeticsunscreen composition) include: PABA (5% or less), camphor benzalkoniummethosulfate (6% or less), homosalate (10% or less), benzophenone-3 (10%or less), phenylbenzimidazole sulfonic acid (8% or less, expressed asacid), terephthalidene dicamphor sulfonic acid (10% or less, expressedas acid), butyl methoxydibenzoylmethane (5% or less), benzylidenecamphor sulfonic acid (6% or less, expressed as acid), octocrylene (10%or less, expressed as acid), polyacrylamidomethyl benzylidene camphor(6% or less), ethylhexyl methoxycinnamate (10% or less), PEG-25 PABA(10% or less), isoamyl p-methoxycinnamate (10% or less), ethylhexyltriazone (5% or less), drometrizole trielloxane (15% or less),diethylhexyl butamido triazone (10% or less), 4-methylbenzylidenecamphor (4% or less), 3-benzylidene camphor (2% or less), ethylhexylsalicylate (5% or less), ethylhexyl dimethyl PABA (8% or less),benzophenone-4 (5%, expressed as acid), methylene bis-benztriazolyltetramethylbutylphenol (10% or less), disodium phenyl dibenzimidazoletetrasulfonate (10% or less, expressed as acid), bis-ethylhexyloxyphenolmethoxyphenol triazine (10% or less), methylene bisbenzotriazolyltetramethylbutylphenol (10% or less, also called TINOSORB M), andbisethylhexyloxyphenol methoxyphenyl triazine. (10% or less, also calledTINOSORB S).

All of the above-described UV filters are commercially available. Forexample, suitable commercially-available organic UV filters areidentified by trade name and supplier in Table I below:

TABLE I CTFA Name Trade Name Supplier benzophenone-3 UVINULM-40 BASFChemical Co. benzophenone-4 UVINUL MS-40 BASF Chemical Co.benzophenone-8 SPECTRA-SORB American Cyanamid UV-24 DEA-methoxycinnamateBERNEL HYDRO Bernel Chemical ethyl dihydroxypropyl-PABA AMERSCREEN PAmerchol Corp. glyceryl PABA NIPA G.M.P.A. Nipa Labs. homosalateKEMESTER HMS Humko Chemical menthyl anthranilate SUNAROME UVA FeltonWorldwide octocrylene UVINUL N-539 BASF Chemical Co. octyl dimethyl PABAAMERSCOL Amerchol Corp. octyl methoxycinnamate PARSOL MCX BernelChemical PABA PABA National Starch 2-phenylbenzimidazole-5- EUSOLEX 6300EM Industries sulphonic acid TEA salicylate SUNAROME W Felton Worldwide2-(4-methylbenzildene)- EUSOLEX 6300 EM Industries camphorbenzophenone-1 UVINUL 400 BASF Chemical Co. benzophenone-2 UVINUL D-50BASF Chemical Co. benzophenone-6 UVINUL D-49 BASF Chemical Co.benzophenone-12 UVINUL 408 BASF Chemical Co. 4-isopropyl dibenzoylEUSOLEX 8020 EM Industries methane butyl methoxy dibenzoyl PARSOL 1789Givaudan Corp. methane etocrylene UVINUL N-35 BASF Chemical Co.methylene bisbenzotriazolyl TINOSORB M Ciba Specialtytetramethylbutylphenol Chemicals bisethylhexyloxyphenol TINOSORB S CibaSpecialty methoxyphenyl triazine. Chemicals

The term “alkyl” as used herein refers to straight- and branched-chainhydrocarbon groups, preferably containing one to thirty carbon atoms.Examples of alkyl groups are C₁-C₄ alkyl groups. As used herein thedesignation C_(x)-C_(y), wherein x and y are integers, denotes a grouphaving from x to y carbon atoms, e.g., a C₁-C₄ alkyl group is an alkylgroup having one to four carbon atoms. Nonlimiting examples of alkylgroups include, methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl(2-methylpropyl), t-butyl(1,1-dimethylethyl), and3,3-dimethylpentane.

The term “cycloalkyl” as used herein refers to an aliphatic cyclichydrocarbon group, preferably containing three to eight carbon atoms.Nonlimiting examples of cycloalkyl groups include cyclopropyl,cyclobutyl, cyclopentyl, and cyclohexyl.

The term “alkenyl” as used herein includes both straight chained,branched, and cyclic hydrocarbon radicals that include at least onecarbon-carbon double bond, preferably, an alkenyl group contains betweentwo and thirty carbon atoms. Nonlimiting examples alkenyl groups includemethylene, ethylene, propylene, butylene, and isopropylene.

The term “alkyne” as used herein includes both straight and branchedchained hydrocarbon radicals having at least one carbon-carbon triplebond, preferably, an alkyne group contains between two and thirty carbonatoms.

The term “polyether” as used herein refers to a group with at least twoethers present in a carbon chain. Nonlimiting examples of polyethersinclude 1-butoxy-2-methoxyethane, 1-butoxy-2-(2-methoxyethoxy)ethane,2-(2-methoxyethoxy)-1-(2-methylpentyloxy)propane, and1-(2-methylpentyloxy)-2-(2-pentyloxyethoxy)propane.

The terms “substituted alkyl,” “substituted cycloalkyl,” “substitutedalkenyl,” “substituted alkyne,” and “substituted polyether” as usedherein refer to an alkyl, cycloalkyl, alkenyl, alkyne, or polyethergroup having one or more substituents. Substituents can include, but arenot limited to, alkyl, cycloalkyl, alkenyl, alkyne, polyether,substituted polyether, heteroaryl, heterocycloalkyl, aryl, substitutedaryl, substituted heteroaryl, substituted heterocycloalkyl, hydroxyl,ester, carboxy, cyano, amino, amido, sulfur, and halo. Preferredsubstituted alkyl groups have one to twenty carbon atoms, not includingcarbon atoms of the substituent group. Preferably, a substituted alkylgroup is mono- or di-substituted at one, two, or three carbon atoms. Thesubstituents can be bound to the same carbon or different carbon atoms.

The term “ester” as used herein refers to a group of the generalformula:

wherein R is an alkyl group, alkenyl group, alkyne group, cycloalkylgroup, polyether, aryl, substituted alkyl group, substituted alkenylgroup, substituted alkyne group, substituted cycloalkyl group,substituted aryl group, substituted heteroaryl, substitutedheterocycloalkyl, or substituted polyether group.

The term “aryl” as used herein refers to monocyclic, fused bicyclic, andfused tricyclic carbocyclic aromatic ring systems including, but notlimited to, phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl,biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl.

The term “heteroaryl” as used herein refers to monocyclic, fusedbicyclic, and fused tricyclic aromatic ring systems, wherein one tofour-ring atoms are selected from the group consisting of oxygen,nitrogen, and sulfur, and the remaining ring atoms are carbon, said ringsystem being joined to the remainder of the molecule by any of the ringatoms. Nonlimiting examples of heteroaryl groups include, but are notlimited to, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl,imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl,oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl,benzoxazolyl, benzimidazolyl, and benzothiazolyl.

The term “heterocycloalkyl” as used herein refers to an aliphatic,partially unsaturated or fully saturated, 3- to 14-membered ring system,including single rings of 3 to 8 atoms and bi- and tricyclic ringsystems. The heterocycloalkyl ring systems include one to fourheteroatoms independently selected from oxygen, nitrogen, and sulfur,wherein a nitrogen and sulfur heteroatom optionally can be oxidized anda nitrogen heteroatom optionally can be substituted. Representativeheterocycloalkyl groups include, but are not limited to, pyrrolidinyl,pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl,piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl,isothiazolidinyl, and tetrahydrofuryl.

The terms “substituted aryl,” “substituted heteroaryl,” and “substitutedheterocycloalkyl” as used herein refer to an aryl, heteroaryl, orheterocycloalkyl group substituted by a replacement of one, two, orthree of the hydrogen atoms thereon with a substitute selected from thegroup consisting of alkyl, alkenyl, alkyne, substituted alkyl,substituted cycloalkyl, substituted alkenyl, substituted alkyne, ether,amino, aryl, heteroaryl, cycloalkyl, heterocycloalkyl, O(CH₂)₁₋₃N(R)₂,O(CH₂)₁₋₃CO₂H, hydroxyl, ester, carboxy, cyano, amino, amido, sulfur,and halo.

The term “amino” as used herein refers to an —NH₂ or —NH— group, whereineach hydrogen in each formula can be replaced with an alkyl, cycloalkyl,aryl, polyether, heteroaryl, heterocycloalkyl, substituted alkyl,substituted cycloalkyl, substituted aryl, substituted polyether,substituted heteroaryl, or substituted heterocycloalkyl group, i.e.,N(R)₂. In the case of —NH₂, the hydrogen atoms also can be replaced withsubstituents taken together to form a 5- or 6-membered aromatic ornon-aromatic ring, wherein one or two carbons of the ring optionally arereplaced with a heteroatom selected from the group consisting of sulfur,oxygen, and nitrogen. The ring also optionally can be substituted withan alkyl group. Examples of rings formed by substituents taken togetherwith the nitrogen atom include morpholinyl, phenylpiperazinyl,imidazolyl, pyrrolidinyl, (N-methyl)piperazinyl, and piperidinyl.

The term “amido” as used herein refers to a moiety of the generalformula:

wherein R¹ and R² are the same or different and selected from hydrogen,alkyl, alkenyl, alkyne, substituted alkyl, substituted alkenyl,substituted alkyne, aryl, alkenyl aryl, heteroaryl, and alkenylheteroaryl.

The term “cyano” as used herein refers to a —C≡N group, also designated—CN.

The term “halo” as used herein refers to fluorine, chlorine, bromine,and iodine.

The term “carboxy” as used herein refers to a moiety of the generalformula:

The term “sulfur” as used herein refers to a neutral sulfur atom that isunsubstituted or substituted with one or more of a neutral species,including any oxidized or reduced form of sulfur (e.g., —SO₂—).Nonlimiting examples of sulfur groups include sulfites, sulfides,sulfates, and alkyl sulfides.

The term “hydroxyl” as used herein refers to an —OH group.

The terms “waterproof” and “waterproofing” as used herein refers to anyincrease in a material/surface's ability to repel water from permeatingthe material/surface. These terms are not intended to mean that amaterial/surface is completely impervious to water, rather, the terms“waterproof” and “waterproofing” are intended to be understood as makinga material/surface less water permeable relative to not having been“waterproofed” or having undergone “waterproofing.”

Ranges may be expressed herein as from “about” or “approximately” oneparticular value and/or to “about” or “approximately” another particularvalue. When such a range is expressed, another embodiment includes fromthe one particular value and/or to the other particular value.Similarly, when values are expressed as approximations, by use of theantecedent “about,” it will be understood that the particular valueforms another embodiment.

A sunscreen composition described herein can include a variety ofphotoactive compounds, including one or more UV-A photoactive compoundsand one or more UV-B photoactive compounds. Preferably, a sunscreencomposition includes a photoactive compound selected from the groupconsisting of p-aminobenzoic acid and salts and derivatives thereof;anthranilate and derivatives thereof; dibenzoylmethane and derivativesthereof; salicylate and derivatives thereof; cinnamic acid andderivatives thereof; dihydroxycinnamic acid and derivatives thereof;camphor and salts and derivatives thereof; trihydroxycinnamic acid andderivatives thereof; dibenzalacetone naphtholsulfonate and salts andderivatives thereof; benzalacetophenone naphtholsulfonate and salts andderivatives thereof; dihydroxy-naphthoic acid and salts thereof;o-hydroxydiphenyldisulfonate and salts and derivatives thereof;p-hydroxydiphenyldisulfonate and salts and derivatives thereof; coumarinand derivatives thereof; diazole derivatives; quinine derivatives andsalts thereof; quinoline derivatives; hydroxy-substituted benzophenonederivatives; methoxy-substituted benzophenone derivatives; uric acidderivatives; vilouric acid derivatives; tannic acid and derivativesthereof; hydroquinone; benzophenone derivatives; 1,3,5-triazinederivatives, phenyldibenzimidazole tetrasulfonate and salts andderivatives thereof; terephthalylidene dicamphor sulfonic acid and saltsand derivatives thereof; methylene bis-benzotriazolyltetramethylbutylphenol and salts and derivatives thereof;bis-ethylhexyloxyphenol methoxyphenyl triazine and salts and derivativesthereof; diethylamino hydroxybenzoyl hexyl benzoate and salts andderivatives thereof; and combinations of the foregoing.

UV-A radiation (about 320 nm to about 400 nm), is recognized ascontributing to causing damage, to skin particularly to verylightly-colored or sensitive skin. A sunscreen composition describedherein preferably includes a UV-A photoactive compound. Preferably, asunscreen composition described herein includes a dibenzoylmethanederivative UV-A photoactive compound. Preferred dibenzoylmethanederivatives include, 2-methyldibenzoylmethane; 4-methyldibenzoylmethane;4-isopropyldibenzoylmethane; 4-tert-butyldibenzoylmethane;2,4-dimethyldibenzoylmethane; 2,5-dimethyldibenzoylmethane;4,4′-diisopropyldibenzoylmethane; 4,4′-dimethoxydibenzoylmethane;4-tert-butyl-4′-methoxydibenzoylmethane;2-methyl-5-isopropyl-4′-methoxydibenzoylmethane;2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane;2,4-dimethyl-4′-methoxydibenzoylmethane;2,6-dimethyl-4-tert-butyl-4′-methoxydibenzoylmethane, and combinationsthereof.

A preferred combination of photoactive compounds in a sunscreencomposition includes a UV-A and a UV-B photoactive compound. However,when 2-ethylhexyl-p-methoxycinnamate is included in a mixture with adibenzoylmethane derivative, the dibenzoylmethane derivative can becomeparticularly unstable. Without intending to be limited to any particularmechanism, it is believed that the cinnamate ester reacts with anexcited-state dibenzoylmethane derivative in a bimolecular pathway thatrenders both the dibenzoylmethane derivative and the cinnamate esterincapable of absorbing UV radiation. It has been found, quitesurprisingly, that the use of a polymer that contains one or morephotoactive compounds (e.g., crylene and/or fluorene moieties)covalently bonded to the polymer backbone increases the stability of asunscreen composition that includes 2-ethylhexyl-p-methoxycinnamate anda dibenzoylmethane derivative. Thus, one embodiment of a sunscreencomposition includes 2-ethylhexyl-p-methoxycinnamate, a dibenzoylmethanederivative, and a polymer that contains one or more photoactivecompounds (e.g., crylene and/or fluorene moieties) covalently bonded tothe polymer backbone.

One embodiment of the compounds, compositions, and methods describedherein is a polymer including monomers selected from the groupconsisting of a monomer of formula (I), a monomer of formula (II), andcombinations thereof:

wherein R¹ and R⁵ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R² and R⁶ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne, aryl,substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryland substituted heterocycloalkyl; R³, R⁴, R⁷ and R⁸ are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether,C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,substituted heteroaryl, substituted heterocycloalkyl, hydroxyl, ester,carboxy, cyano, amino, amido, sulfur and halo; b, c, e and f are each inthe range of 0 to 4; a and d are each in the range of 0 to 200, and thesum of a and d is at least 1. Preferably, R² and R⁶ are the same ordifferent and are selected from the group consisting of C₂-C₁₅ alkylgroups, more preferably they are the same and are 2,2-dimethylpropane.Preferably, R¹ and R⁵ are the same or different and are selected fromthe group consisting of C₅-C₂₅ alkyl groups, more preferably they arethe same and are C₁₆ straight chain alkyl groups.

Polymers including monomers of formula (I) and/or formula (II), quitesurprisingly, are able to increase the stability of a photoactivecompound in a sunscreen composition. Accordingly, another embodiment ofcompounds, compositions, and methods described herein is a sunscreencomposition sunscreen composition, including a mixture of a photoactivecompound, and a polymer including monomers selected from the groupconsisting of a monomer of formula (I), a monomer of formula (II), andcombinations thereof:

wherein R¹ and R⁵ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R² and R⁶ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne, aryl,substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryland substituted heterocycloalkyl; R³, R⁴, R⁷ and R⁸ are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether,C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,substituted heteroaryl, substituted heterocycloalkyl, hydroxyl, ester,carboxy, cyano, amino, amido, sulfur and halo; b, c, e and f are each inthe range of 0 to 4; a and d are each in the range of 0 to 200, and thesum of a and d is at least 1. Preferably, R² and R⁶ are the same ordifferent and are selected from the group consisting of C₂-C₁₅ alkylgroups, more preferably they are the same and are 2,2-dimethylpropane.Preferably, a polymer including monomers selected from the groupconsisting of a monomer of formula (I), a monomer of formula (II), andcombinations thereof is present in a sunscreen composition in a range ofabout 0.01% to about 30% by weight of the total weight of thecomposition, more preferably in a range of about 0.1% to about 10%.

Polymers including monomers of formula (I) and/or monomers of formula(II), quite surprisingly, are able to absorb UV-radiation and toincrease the photostability of a photoactive compound in a sunscreencomposition, the polymers are therefore able to be used to protect asurface (e.g., human skin) from the harmful effects of UV-radiation.FIG. 1 shows the absorbance spectra from 280 nm to 400 nm for asunscreen composition wherein Octadecene/Crylene maleate copolymer (apolymer with monomers selected from the monomers of formulae (I) and(II) wherein R¹ and R⁵ is a C₁₆ straight chain alkyl group, R² and R⁶ isa 2,2-dimethylpropyl group, and there is no substitution of the aromaticrings of the crylene moieties) is present as the only UV-absorbingcompound. FIG. 2 is a graph of the absorbance spectra from 280 nm to 400nm for the sunscreen compositions shown in Table III, and thecomposition shown in Table II, wherein Octadecene/Crylene maleatecopolymer is included as the only UV-absorbing compound. FIG. 2 confirmsthat Octadecene/Crylene maleate copolymer absorbs UV-radiationindependent of other UV-absorbing agents that may be present in asunscreen composition. FIG. 11 shows the absorbance spectra from 280 nmto 400 nm for a sunscreen composition that contains 2% Crylene/CetylPolymer (a polymer containing the monomers containing crylene moieties(as shown in formulae (I) and (II) wherein R² and R⁶ are2,2-dimethylpropane, and R¹ and R⁵ are C₁₆ straight chain alkyl groups)and monomers that contain C₁₆ fatty esters (as shown in formulae (III)and (IV) wherein R⁹ and R¹¹ are C₁₆ straight chain alkyl groups, and R¹⁰and R¹² are C₁₆ straight chain alkyl groups), and for a composition thatcontains 0% of the Crylene/Cetyl Polymer (see Table VI for the sunscreenformulations). As shown in FIG. 11, the sunscreen composition that doesincludes 2% of the Crylene/Cetyl Polymer achieves the highest absorbanceas compared to the sunscreen composition of Table VI that does notinclude the polymer. FIG. 12 shows the absorbance spectra from 280 nm to400 m for a sunscreen composition that contains 2% Crylene/BehenylPolymer (a polymer containing the monomers containing crylene moieties(as shown in formulae (I) and (II) wherein R² and R⁶ are2,2-dimethylpropane, and R¹ and R⁵ are C₁₆ straight chain alkyl groups)and monomers that contain C₁₆ fatty esters (as shown in formulae (III)and (IV) wherein R⁹ and R¹¹ are C₁₆ straight chain alkyl groups, and R¹⁰and R¹² are C₂₂ straight chain alkyl groups), and for a composition thatcontains 0% of the Crylene/Behenyl Polymer (see Table VIII for thesunscreen formulations). As shown in FIG. 12, the sunscreen compositionthat does includes 2% of the Crylene/Behenyl Polymer achieves thehighest absorbance as compared to the sunscreen composition of TableVIII that does not include the polymer. Accordingly, another embodimentof the compounds, compositions and methods described herein is a methodof protecting a surface from ultraviolet radiation, including topicallyapplying to the surface, in a cosmetically acceptable carrier, a polymerincluding monomers selected from the group consisting of a monomer offormula (I), a monomer of formula (II), and combinations thereof:

wherein R¹ and R⁵ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R² and R⁶ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne, aryl,substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryland substituted heterocycloalkyl; R³, R⁴, R⁷ and R⁸ are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether,C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,substituted heteroaryl, substituted heterocycloalkyl, hydroxyl, ester,carboxy, cyano, amino, amido, sulfur and halo; b, c, e and f are each inthe range of 0 to 4; a and d are each in the range of 0 to 200, and thesum of a and d is at least 1. Polymers including a monomer of formula(I) and/or formula (II) may be used to protect human skin from theharmful effects of ultra-violet radiation, and thus, the preferredsurface for use of the polymers described herein is human skin.Preferably, R² and R⁶ are the same or different and are selected fromthe group consisting of C₂-C₁₅ alkyl groups, more preferably R² and R⁶are the same and are 2,2-dimethylpropane.

It has been found that polymers that include a monomer of formula (I)and/or a monomer of formula (II) may be used to waterproof a surface,and thereby, make the surface less water permeable. This aspect of apolymer including monomers of formulae (I) and/or (II) may be used in avariety of applications, including a sunscreen composition. A polymerincluding monomers of formulae (I) and/or (II) may be added to asunscreen composition to help prevent the loss of the composition thatmay accompany the immersion in water of the object (e.g., human skin)that has been applied with the composition. Accordingly, anotherembodiment of the compounds, compositions and methods described hereinis a method of waterproofing a surface, including applying a polymerincluding monomers selected from the group consisting of a monomer offormula (I), a monomer of formula (II), and combinations thereof to aselected area of the surface:

wherein R¹ and R⁵ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R² and R⁶ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne, aryl,substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryland substituted heterocycloalkyl; R³, R⁴, R⁷ and R⁸ are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether,C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,substituted heteroaryl, substituted heterocycloalkyl, hydroxyl, ester,carboxy, cyano, amino, amido, sulfur and halo; b, c, e and f are each inthe range of 0 to 4; a and d are each in the range of 0 to 200, and thesum of a and d is at least 1. Polymers including a monomer of formula(I) and/or formula (II) is preferably be used in a sunscreen compositionas a waterproofing agent to avoid the loss of composition when thecomposition is immersed in water. Thus, the preferred surface for use ofa polymer is human skin. Preferably, R² and R⁶ are the same or differentand are selected from the group consisting of C₂-C₁₅ alkyl groups, morepreferably R² and R⁶ are the same and are 2,2-dimethylpropane.

It has also been found that a polymer including monomers of formulae (I)and/or (II) may be used to form a film on a surface, and when added to acomposition, a polymer including monomers of formulae (I) and/or (II)may provide film-forming properties to the composition. Accordingly,another embodiment of the compounds, compositions and methods describedherein is a method for forming a film over at least part of a surface,including spreading a polymer including monomers selected from the groupconsisting of a monomer of formula (I), a monomer of formula (II), andcombinations thereof on a part of the surface:

wherein R¹ and R⁵ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R² and R⁶ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne, aryl,substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryland substituted heterocycloalkyl; R³, R⁴, R⁷ and R⁸ are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether,C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,substituted heteroaryl, substituted heterocycloalkyl, hydroxyl, ester,carboxy, cyano, amino, amido, sulfur and halo; b, c, e and f are each inthe range of 0 to 4; a and d are each in the range of 0 to 200, and thesum of a and d is at least 1. Polymers including a monomer of formula(I) and/or formula (II) may be used to form a film on human skin tospread photoactive compounds in a sunscreen composition onto the skin.Thus, the preferred surface is human skin. Preferably, R² and R⁶ are thesame or different and are selected from the group consisting of C₂-C₁₅alkyl groups, more preferably R² and R⁶ are the same and are2,2-dimethylpropane.

Likewise, a polymer including monomers of formulae (I) and/or (II),quite surprisingly, is able to increase the photostability of adibenzoylmethane derivative. Without intending to be limited to aparticular mechanism, it is believed that a polymer including monomersselected from the group consisting of a monomer of formula (I), amonomer of formula (II), and combinations thereof is able tophotostabilize a dibenzoylmethane derivative by accepting the tripletexcited energy from an excited dibenzoylmethane derivative. Thus,another embodiment of the compounds, compositions, and methods describedherein is to provide a method of photostabilizing a dibenzoylmethanederivative, the method including the step of, adding to thedibenzoylmethane derivative a photostabilizing amount of a polymerincluding monomers selected from the group consisting of a monomer offormula (I), a monomer of formula (II), and combinations thereof:

wherein R¹ and R⁵ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R² and R⁶ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne, aryl,substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryland substituted heterocycloalkyl; R³, R⁴, R⁷ and R⁸ are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether,C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,substituted heteroaryl, substituted heterocycloalkyl, hydroxyl, ester,carboxy, cyano, amino, amido, sulfur and halo; b, c, e and f are each inthe range of 0 to 4; a and d are each in the range of 0 to 200, and thesum of a and d is at least 1. Preferably, R² and R⁶ are the same ordifferent and are selected from the group consisting of C₂-C₁₅ alkylgroups, more preferably R² and R⁶ are the same and are2,2-dimethylpropane.

EXAMPLES

The following examples are provided to illustrate the compounds,compositions, and methods described herein but are not intended to limitthe scope of the compounds, compositions, and methods described herein.

Example 1

The following is a preparation for a polymer compound containing crylenemoieties attached to the polymer backbone, whereinPoly(octadecene-1-co-maleic anhydride) resin (PA-18 available fromChevron Chemicals Co., San Francisco, Calif.) served as a polymerstarting material, and2,2-dimethyl-3-hydroxypropyl-2-cyano-3,3-diphenylpropenoate served asthe crylene moiety with a tether of neopentyl glycol. The PA-18Polyanhydride Resin (300 g) and2,2-dimethyl-3-hydroxypropyl-2-cyano-3,3-diphenylpropenoate (258 g) wereplaced in 2 L 3-neck round-bottom flask and 800 ml of toluene was added.The reaction mixture was then heated and refluxed for two hours untilreaction was completed (as determined by GPC). The product in solutionwas placed in evaporation vessels to remove the solvent. The finalproduct was then dried and ground to give off-white powder (510 g, 91%yield).

Example 2

The following is a preparation for a polymer compound containing crylenemoieties and a fatty ester (a C₁₆ straight chain carbon) attached to thepolymer backbone, wherein Poly(octadecene-1-co-maleic anhydride) resin(PA-18 available from Chevron Chemicals Co., San Francisco, Calif.)served as a polymer starting material,2,2-dimethyl-3-hydroxypropyl-2-cyano-3,3-diphenylpropenoate served asthe crylene moiety with a tether of neopentyl glycol, and cetyl alcohol(available from Sigma-Aldrich, St. Louis, Mo.) attached to the backboneto create a fatty ester moiety. The polymer produced by theforegoing-procedure includes the following monomers dispersed throughoutthe polymer:

It is also expected that a small amount of the unreacted anhydridemonomers and/or unreacted diacid monomers that correspond to theanhydride monomer starting material (PA-18 polymer) will be present inthe final polymer composition.

The polymer was prepared by placing the 200 g of the PA-18 polymer (1mole equivalence) and 114.82 g of 2,2-dimethyl-3-hydroxypropyl2-cyano-3,3-diphenylpropenoate (0.342 moles, 0.6 mole equivalence) in a2-liter 3-neck round-bottom flask, assembled with Dean-Stark receiver,and 1000 ml of xylenes were added to the flask. A heterogeneous reactionmixture was created, and the mixture was brought to boiling and refluxedfor two hours to remove any traces of water. After the mixture wasrefluxed for two hours, a first portion of TYZOR DEA (0.5 g) (availablefrom Dupont, Wilmington, Del.) was added to the reaction mixture. Thereaction mixture was allowed to reflux for an additional six hours, andthen the reaction mixture was cooled to room temperature and allowed tostir at room temperature for ten hours.

To the room temperature reaction mixture 27.64 g of cetyl alcohol (0.114mole, 0.2 mole-equivalence) was added and the mixture was refluxed forone hour. A second portion of TYZOR DEA (0.5 g) was then added, thereaction mixture was allowed to reflux for an additional seven hours,and following the reflux, the reaction mixture was cooled to roomtemperature. The reaction mixture was transferred to a drying vessel andthe solvent was removed under reduced pressure.

A GPC analysis of the solid product showed nearly full incorporation ofboth the crylene moiety and the cetyl alcohol into the polymer with only0.1% of free crylene moiety (2,2-dimethyl-3-hydroxypropyl2-cyano-3,3-dipthenylpropenoate) present in the product. The polymericproduct (313.7 g; 92% of the theoretical yield) was powdered beforefurther application.

Example 3

The following is a preparation for a polymer compound containing crylenemoieties and a fatty ester (a C₂₂ straight chain carbon) attached to thepolymer backbone, wherein Poly(octadecene-1-co-maleic anhydride) resin(PA-18 available from Chevron Chemicals Co., San Francisco, Calif.)served as a polymer starting material,2,2-dimethyl-3-hydroxypropyl-2-cyano-3,3-diphenylpropenoate served asthe crylene moiety with a tether of neopentyl glycol, and 1-Docosanol(behenyl alcohol)(available from Sigma-Aldrich, St. Louis, Mo.) attachedto the backbone to create a fatty ester moiety. The polymer produced bythe foregoing procedure includes the following monomers dispersedthroughout the polymer:

It is also expected that a small amount of the unreacted anhydridemonomers and/or unreacted diacid monomers that correspond to theanhydride monomer starting material (PA-18 polymer) will be present inthe final polymer composition.

The polymer was prepared by placing the 200 g of the PA-18 polymer (1mole equivalence) and 114.82 g of 2,2-dimethyl-3-hydroxypropyl2-cyano-3,3-diphenylpropenoate (0.342 moles, 0.6 mole equivalence) in a2-liter 3-neck round-bottom flask, assembled with Dean-Stark receiver,and 1000 ml of xylenes were added to the flask. A heterogeneous reactionmixture was created, and the mixture was brought to boiling and refluxedfor two hours to remove any traces of water. After the mixture wasrefluxed for two hours, a first portion of TYZOR DEA (0.63 g) (availablefrom Dupont, Wilmington, Del.) was added to the reaction mixture, andthe reaction mixture was allowed to reflux for an additional six hours.A second portion of TYZOR DEA (0.63 g) was then added to the reactionmixture and the reaction mixture a refluxed for an additional 10 hours.

To the refluxing reaction mixture, 17.58 g of 1-Docosanol (behenylalcohol) (0.054 mole, 0.1 mole-equivalence) was added and the mixturewas refluxed for one hour. A second portion of TYZOR DEA (0.63 g) wasthen added, the reaction mixture was allowed to reflux for an additionalseven hours, and following the reflux, the reaction mixture was cooledto room temperature. The reaction mixture was transferred to a dryingvessel and the solvent was removed under reduced pressure.

A GPC analysis of the solid product showed nearly full incorporation ofboth the crylene moiety and the cetyl alcohol into the polymer with only0.1% of free crylene moiety (2,2-dimethyl-3-hydroxypropyl2-cyano-3,3-dipthenylpropenoate) present in the product. The polymericproduct (293 g; 93% of the theoretical yield) was powdered beforefurther application.

Example 4

A composition which included only the Octadecene/Crylene maleatecopolymer as the only UV-Absorbing compound was prepared by mixing theingredients shown in Table II below:

TABLE II Weight Phase Ingredient Percent A Caprylic/capric triglycerides8.00% Polyisobutene 3.00% Phenylethyl benzoate 1.00% Diethylhexyl malate2.00% B Octadecene/Crylene maleate copolymer 2.00% C Stearyl alcohol1.00% Steareth-21 0.22% Steareth-2 0.28% Polyglyceryl-3 methyl glucosedistearate 3.00% D Dimethicone (100 cSt) 0.40% E Water 72.56% DisodiumEDTA 0.05% Carbomer 0.20% F Sorbitol (70%) 4.29% Phenoxyethanol,Methylparaben, Ethylparaben, 1.00% Propylparaben, and IsobutylparabenTriethanolamine 1.00%

An oil-in-water emulsion was created, wherein the aqueous phase includeda mixture of the ingredients in Phase E, and the oil phase included amixture of the ingredients of Phases A, B, C, and D. The emulsion wasprepared by combining the ingredients of Phase A, and adding thismixture of ingredients to a vessel, and heating the vessel to about 90°C. The ingredients from Phases B, C, and D were then added to the heatedvessel with stirring until the mixture became clear and homogeneous. Inanother vessel, the ingredients of Phase E were added in the order shownin Table II, with continuous stirring. The vessel containing theingredients of Phase E was then heated to about 80° C. Withhomogenization, the contents of the vessel containing the oil phase (amixture of the ingredients of Phases A, B, C, and D) were added to thevessel containing the water phase (a mixture of the ingredients of PhaseE). The resulting mixture was homogenized for three minutes, and thenthe vessel was remove from heat source and allowed to cool. When thetemperature of the mixture fell below 40° C., the ingredients of Phase Fwere added. The mixture was stirred until a smooth cream was formed. Theresulting cream was then packaged to avoid the inadvertentphotodegradation of the UV-absorbing compounds in the composition.

FIG. 1 is a graph of the percent absorbance of the sunscreen compositionlisted in Table II. As shown in FIG. 1, the Octadecene/Crylene maleatecopolymer absorbs over the entire UV-spectrum, but achieves its maximumabsorbance in the range of about 290-330 nm.

Example 5

Two sunscreen compositions were prepared by mixing the ingredients shownin Table III below:

TABLE III Sunscreen w/0% Sunscreen w/2% Phase Ingredient Polymer (wt. %)Polymer (wt. %) A Octyl salicylate  5.00%  5.00% Homosalate  7.50% 7.50% Diethylhexyl 2,6-  2.50%  2.50% naphthalate Octocrylene  2.50% 2.50% Dimethyl capramide  1.00%  1.00% Diethylhexyl malate  2.01% 2.01% B Avobenzone  3.00%  3.00% Benzophenone-3  0.49%  0.49% COctyldodecanol  2.00% Octadecene/Crylene  2.00% maleate copolymer DStearyl alcohol  1.00%  1.00% Steareth 21  0.29%  0.29% Steareth 2 0.21%  0.21% Polyglyceryl-3 methyl  3.00%  3.00% glucose distearate EWater 64.16% 63.16% Disodium EDTA  0.05%  0.05% Carbomer  0.20%  0.20%Sorbitol (70%)  4.29%  4.29% Phenoxyethanol,  0.60%  0.60%Methylparaben, Ethylparaben, Propylparaben, and Isobutylparaben FTriethanolamine  0.2%  1.2%

Oil-in-water emulsions were created, wherein the aqueous phase includeda mixture of the ingredients in Phase E, and the oil phase included amixture of the ingredients of Phases A, B, C, and D. The emulsions wereprepared by combining the ingredients of Phase A, and adding thismixture of ingredients to a vessel, and heating the vessel to about 90°C. The ingredients from Phases B, C, and D were then added to the heatedvessel with stirring until the mixture became clear and homogeneous. Inanother vessel, the ingredients of Phase E were added in the order shownin Table III, with continuous stirring. The vessel containing theingredients of Phase E was then heated to about 80° C. Withhomogenization, the contents of the vessel containing the oil phase (amixture of the ingredients of Phases A, B, C, and D) to the vesselcontaining the water phase (a mixture of the ingredients of Phase E).The resulting mixture was homogenized for three minutes, and then thevessel was remove from heat source and allowed to cool. When temperatureof the mixture fell below 40° C., the ingredient of Phase F(triethanolamine) was added. The mixture was stirred until a smoothcream was formed. The resulting creams were packaged to avoid theinadvertent photodegradation of the UV-absorbing compounds, and thecreams were then used to test the photostability of the compositions.

The resulting sunscreens were tested for photostability by measuringabsorbance on a Labsphere UV-1000S Ultraviolet Transmittance Analyzer(software version 1.27) before and after irradiation with a Solar LightCompany model 16S solar simulator (equipped with a UG11 filter to blockradiation greater than 400 nm, WG320 filter that transmits UV-radiationgreater than 290 nm), and a removable WG335 filter that transmitsUV-radiation greater than 320 nm). Output was monitored by a PMA 2105UV-B DCS Detector (biologically weighted) or a PMA 2114 UV-A Detectorand controlled by a PMA 2100 Automatic Dose Controller (available fromSolar Light Co.).

To test stability, a synthetic skin substrate was used for testing thesunscreen compositions (VITRO-SKIN substrate (Lot No. 3059) by IMS, Inc.of Milford, Conn.). To prepare the substrate, a 300 g solution of 18 wt.% glycerin and 82 wt. % deionized water was added to a hydrating chamber(IMS), and a sheet of VITRO-SKIN was placed in the hydrating chamber andleft overnight (approx. 16 hours). Several 6.5 cm squares were cut fromthe hydrated VITRO-SKIN and used for absorbance measurements.

To prepare slides for testing, a minimum 100 μl of sunscreen compositionis drawn or placed into a pipet tip (Justor 1100DG, set to dispense 100μl). Using steady, even pressure on the pipette plunger, the testsubstance was applied to VITRO-SKIN square in a pattern of at least 50small dots arranged to cover a 6 cm center of a square. The VITRO-SKINsquare was then placed on a foam block, and the test material was spreadby finger (covered with a latex glove or finger cot), first in acircular motion, then by a side-to-side motion during which theVITRO-SKIN is deformed by the pressure. The square was then mounted in aslide holder (60 mm×60 mm glassless slide mounts with metal masks byGepe Management AG, Zug, Switzerland) and allowed to dry for 30-60minutes.

It has been found that to avoid certain errors of an as yet unknowncause, it is advantageous to pre-expose the tested spot on the slide to2 MED, and then zero the detector to treat the pre-exposed spot as a 0MED reading. Thus, using the PMA 2105 UV-B detector, a pre-exposure of 2MED was made. Immediately following the pre-exposure, the slide is takento the UV Transmittance Analyzer and the irradiated spot is scanned. Theoriginal scan is deleted, and the new scan is saved as the baseline (“0MED”) scan.

To test stability of a slide in the UV-B range, the PMA 2105 was used,and the slide was positioned on the UV transmittance analyzer usingregistration marks, and a scan of a 1 cm spot on the slide wasperformed. The slide was then transferred to a holder placed adjacent tothe solar simulator and, using a calipers, was positioned such that thebeam of UV radiation exiting the solar simulator illuminated the same 1cm spot on the slide. To test stability of a slide in the UV-A range,the PMA 2114 was substituted for the PMA 2105, and a WG335 filter wasinstalled in the beam path. The following software settings were used:UV-B=290-320 nm; UV-A=320-400 nm. Following an exposure of 5 MED, theslide was again placed in position on the UV transmittance analyzer, anda scan of the exposed spot was performed. The procedure was repeated onthe same 1 cm spot on the slide until the desired total radiation dosagewas achieved (approximately 35 MED for the UV-B studies, and 120 J/cm²for the UV-A studies).

FIG. 2 is a graph of the absorbance of the composition listed in TableII and the sunscreen compositions listed in Table III. As shown in FIG.2, the sunscreen composition that does includes 2% of theOctadecene/Crylene maleate copolymer achieves the highest absorbance ascompared to the sunscreen composition of Table III that does not includethe polymer and the composition of Table II that includes 2% of thepolymer as the only UV-absorber.

FIG. 3 is a graph of the absorbance of the sunscreen composition listedin Table III, which has no Octadecene/Crylene maleate copolymer in thecomposition. The absorbance spectra of the composition was recordedbefore and after exposure to 35 MED of radiation. As shown in FIG. 3,the sunscreen composition that does not include the Octadecene/Crylenemaleate copolymer is susceptible to photodegradation at 35 MED exposure.

FIG. 4 is a graph of the absorbance of the sunscreen composition listedin Table III that includes 2% of the Octadecene/Crylene maleatecopolymer in the composition. The absorbance spectra of the compositionwas recorded before and after exposure to 35 MED of radiation. As shownin FIG. 4, the absorbance spectra of the sunscreen composition of TableIII that includes 2% of the Octadecene/Crylene maleate copolymer showsthat the composition is relatively stable to photodegradation uponexposure to up to 35 MED.

FIG. 5 is a graph of the absorbance of the both sunscreen compositionslisted in Table III, including one that includes 2% of theOctadecene/Crylene maleate copolymer, and one that does not include theOctadecene/Crylene maleate copolymer. The absorbance spectra ofcompositions were recorded before and after exposure to 35 MED ofradiation. As shown in FIG. 4, the Octadecene/Crylene maleate copolymerincreases the photostability of the composition.

FIGS. 6 and 7 are the absorbance spectra for the compositions listed inTable III.

Example 6

A determination of the Sun Protection Factor (SPF) of the sunscreencompositions listed in Table II and Table III was performed. To test theSPF of the compositions, each slide was placed on the UV transmittanceanalyzer and scans were taken from five locations on the slide. An SPFreport was generated for each slide using the Labsphere softwareUV1000S, Version 1.27.

The results of the SPF testing for the composition listed in Table IIand the compositions listed in Table III are shown below in Table IV:

TABLE IV Composition SPF Results Composition with 2% Scan No. 1 4.65Polymer as the only UV- Scan No. 2 4.68 Absorbing Compound Scan No. 35.04 (Table II) Scan No. 4 5.17 Scan No. 5 4.89 Average SPF 4.9Sunscreen Composition Scan No. 1 23.32 with 0% Polymer Scan No. 2 21.98(Table III) Scan No. 3 18.96 Scan No. 4 23.35 Scan No. 5 21.88 AverageSPF 21.9 Sunscreen Composition Scan No. 1 25.78 with 2% Polymer Scan No.2 27.90 (Table III) Scan No. 3 26.96 Scan No. 4 27.64 Scan No. 5 25.83Average SPF 26.8

The results shown in Table IV indicate that the addition of 2%Octadecene/Crylene maleate copolymer to a topical composition thecontains no other UV absorbers provides an SPF of about 5, and providesan increase in SPF of about 5 to sunscreen compositions.

Example 7

The water resistance of sunscreen compositions listed in Table III wastested by immersing slides of VITRO-SKIN, which contain thecompositions, in moving water for a period of time and testing theslides for a loss in absorbance as measured by SPF. The slides weretested before and after being immersed in water and the results werecompared.

The slides were prepared according to the procedure set forth in Example5, and each slide was placed in a beaker and the top, bottom, and sidesof the slides were secured in the beaker with binder clips. The slideswere then completely immersed in water by the addition of two liters oftap water to the beaker. The beaker was placed on a stir table and astir bar is placed on the bottom of the beaker. The stir bar is set inmotion to circulate the water with a mild vortex. After 40 minutes, theslides were removed from the beaker, shaken to remove excess water, andallowed to air-dry for 30 minutes. Scans are taken from five locationson the slides. The absorbance spectra and an SPF report was generatedfor each composition.

The results of the SPF reports are summarized in Table V below:

TABLE V Pre-Immersion Post-Immersion Composition SPF Results SPF ResultsSunscreen Composition Scan No. 1 23.58 12.10 with 0% Polymer Scan No. 222.39 10.73 (Table III) Scan No. 3 19.81 9.69 Scan No. 4 24.11 12.57Scan No. 5 21.17 11.07 Average SPF 22.2 11.2 Sunscreen Composition ScanNo. 1 27.09 29.08 with 2% Polymer Scan No. 2 27.77 29.45 (Table III)Scan No. 3 27.23 29.10 Scan No. 4 27.29 29.42 Scan No. 5 27.74 28.30Average SPF 27.4 29.1

As shown in Table V, the immersion of the sunscreen compositioncontaining 0% of the Octadecene/Crylene maleate copolymer in watercauses a significant loss of SPF. In contrast, when the sunscreencomposition listed in Table III that included 2% Octadecene/Crylenemaleate copolymer was immersed in water, there was actually a slightincrease in the SPF results as compared to the pre-immersion SPFresults. We consider this increase to be anomalous and withoutsignificance. However, this test and the others referenced in theaccompanying demonstrate the polymer's ability to: (a) provide waterresistance (i.e., water proofing) to the composition, and therebyavoiding loss of the composition upon immersion; (2) absorbUV-radiation; and (3) stabilize the other photoactive compounds in thecomposition by, for example, absorbing the excited state energy of otherphotoactive compounds and rapidly dissipating that energy.

FIG. 8 is a graph of the absorbance of the sunscreen composition listedin Table III where there is no Octadecene/Crylene maleate copolymer inthe composition. As shown in FIG. 8, there is a significant loss inabsorbance after the composition has been immersed in moving water for40 minutes.

FIG. 9 is a graph of the absorbance of the sunscreen composition listedin Table III that included 2% Octadecene/Crylene maleate copolymer inthe composition. As shown in FIG. 9, the absorbance spectra indicatesthat the immersion of the composition in moving water for 40 minutesdoes not cause a loss in the absorbance over the entire UV-spectra(290-400 nm).

FIG. 10 is a graph of the percent absorbance of both of the sunscreencompositions listed in Table III. As shown in FIG. 10, as compared tothe composition that does not include the Octadecene/Crylene maleatecopolymer, the addition of the Octadecene/Crylene maleate copolymer tothe composition prevents a loss in absorbance upon immersion in movingwater for 40 minutes.

Example 8

Sunscreen compositions where prepared that included 2% of the polymerprepared in Example 2 (as shown in formulae (I) and (II) wherein R² andR⁶ are 2,2-dimethylpropane, and R¹ and R⁵ are C₁₆ straight chain alkylgroups) and monomers that contain C₁₆ fatty esters (as shown in formulae(III) and (IV) wherein R⁹ and R¹¹ are C₁₆ straight chain alkyl groups,and R¹⁰ and R¹² are C₁₆ straight chain alkyl groups), which shall bereferred to throughout the examples as “Crylene/Cetyl Polymer,” and thatsubstituted the Crylene/Cetyl Polymer with the non-UV absorbingOctyldodecanol using the ingredients listed in Table VI below:

TABLE VI Sunscreen w/0% Sunscreen w/2% Phase Ingredient Polymer (wt. %)Polymer (wt. %) A Octyl salicylate  5.00%  5.00% Homosalate  7.50% 7.50% Dimethyl capramide  1.00%  1.00% Diethylhexyl malate  2.00% 2.00% B Avobenzone  3.00%  3.00% C Octyldodecanol  2.00% Crylene/Cetylcopolymer  2.00% D Stearyl alcohol  1.00%  1.00% Steareth 21  0.29% 0.29% Steareth 2  0.21%  0.21% Polyglyceryl-3 methyl  3.00%  3.00%glucose distearate E Water 69.66% 68.66% Disodium EDTA  0.05%  0.05%Carbomer  0.20%  0.20% Sorbitol (70%)  4.29%  4.29% Phenoxyethanol, 0.60%  0.60% Methylparaben, Ethylparaben, Propylparaben, andIsobutylparaben F Triethanolamine  0.2%  1.2%

Oil-in-water emulsions were created, wherein the aqueous phase includeda mixture of the ingredients in Phase E, and the oil phase included amixture of the ingredients of Phases A, B, C, and D. The emulsions wereprepared by combining the ingredients of Phase A, and adding thismixture of ingredients to a vessel, and heating the vessel to about 90°C. The ingredients from Phases B, C, and D were then added to the heatedvessel with stirring until the mixture became clear and homogeneous. Inanother vessel, the ingredients of Phase E were added in the order shownin Table VI, with continuous stirring. The vessel containing theingredients of Phase E was then heated to about 80° C. Withhomogenization, the contents of the vessel containing the oil phase (amixture of the ingredients of Phases A, B, C, and D) to the vesselcontaining the water phase (a mixture of the ingredients of Phase E).The resulting mixture was homogenized for three minutes, and then thevessel was remove from heat source and allowed to cool. When temperatureof the mixture fell below 40° C., the ingredient of Phase F(triethanolamine) was added. The mixture was stirred until a smoothcream was formed. The resulting creams were packaged to avoid theinadvertent photodegradation of the UV-absorbing compounds, and thecreams were then used to test the photostability of the compositions.

The resulting sunscreens were tested for photostability by measuringabsorbance on a Labsphere UV-1000S Ultraviolet Transmittance Analyzer(software version 1.27) before and after irradiation with a Solar LightCompany model 16S solar simulator (equipped with a UG11 filter to blockradiation greater than 400 nm, WG320 filter that transmits UV-radiationgreater than 290 nm), and a removable WG335 filter that transmitsUV-radiation greater than 320 nm). Output was monitored by a PMA 2105UV-B DCS Detector (biologically weighted) or a PMA 2114 UV-A Detectorand controlled by a PMA 2100 Automatic Dose Controller (available fromSolar Light Co.).

To test stability, a synthetic skin substrate was used for testing thesunscreen compositions (VITRO-SKIN substrate (Lot No. 3059) by IMS, Inc.of Milford, Conn.). To prepare the substrate, a 300 g solution of 18 wt.% glycerin and 82 wt. % deionized water was added to a hydrating chamber(IMS), and a sheet of VITRO-SKIN was placed in the hydrating chamber andleft overnight (approx. 16 hours). Several 6.5 cm squares were cut fromthe hydrated VITRO-SKIN and used for absorbance measurements.

To prepare slides for testing, a minimum 100 μl of sunscreen compositionis drawn or placed into a pipet tip (Justor 1100DG, set to dispense 100μl). Using steady, even pressure on the pipette plunger, the testsubstance was applied to VITRO-SKIN square in a pattern of at least 50small dots arranged to cover a 6 cm center of a square. The VITRO-SKINsquare was then placed on a foam block, and the test material was spreadby finger (covered with a latex glove or finger cot), first in acircular motion, then by a side-to-side motion during which theVITRO-SKIN is deformed by the pressure. The square was then mounted in aslide holder (60 mm×60 mm glassless slide mounts with metal masks byGepe Management AG, Zug, Switzerland) and allowed to dry for 30-60minutes.

It has been found that to avoid certain errors of an as yet unknowncause, it is advantageous to pre-expose the tested spot on the slide to2 MED, and then zero the detector to treat the pre-exposed spot as a 0MED reading. Thus, using the PMA 2105 UV-B detector, a pre-exposure of 2MED was made. Immediately following the pre-exposure, the slide is takento the UV Transmittance Analyzer and the irradiated spot is scanned. Theoriginal scan is deleted, and the new scan is saved as the baseline (“0MED”) scan.

To test stability of a slide in the UV-B range, the PMA 2105 was used,and the slide was positioned on the UV transmittance analyzer usingregistration marks, and a scan of a 1 cm spot on the slide wasperformed. The slide was then transferred to a holder placed adjacent tothe solar simulator and, using a calipers, was positioned such that thebeam of UV radiation exiting the solar simulator illuminated the same 1cm spot on the slide. To test stability of a slide in the UV-A range,the PMA 2114 was substituted for the PMA 2105, and a WG335 filter wasinstalled in the beam path. The following software settings were used:UV-B=290-320 nm; UV-A=320-400 nm. Following an exposure of 5 MED, theslide was again placed in position on the UV transmittance analyzer, anda scan of the exposed spot was performed. The procedure was repeated onthe same 1 cm spot on the slide until the desired total radiation dosagewas achieved (approximately 35 MED for the UV-B studies, and 120 J/cm²for the UV-A studies).

FIG. 11 is a graph of the absorbance of the sunscreen compositionslisted in Table VI. As shown in FIG. 11, the sunscreen composition thatdoes includes 2% of the Crylene/Behenyl Polymer achieves the highestabsorbance as compared to the sunscreen composition of Table VI thatdoes not include the polymer.

Example 9

A determination of the Sun Protection Factor (SPF) of the sunscreencompositions that were prepared in Example 8 was performed. To test theSPF of the compositions, each slide was placed on the UV transmittanceanalyzer and scans were taken from five locations on the slide. An SPFreport was generated for each slide using the Labsphere softwareUV1000S, Version 1.27.

The results of the SPF testing for the composition listed in Table VIIare shown below in Table VII:

TABLE VII Composition SPF Results Sunscreen Composition Scan No. 1 17.06with 0% Polymer Scan No. 2 6.60 (Table VI) Average SPF 11.83 SunscreenComposition Scan No. 1 17.52 with 2% Polymer Scan No. 2 13.65 (Table VI)Average SPF 15.59

The results shown in Table VII indicate that the addition of 2%Crylene/Cetyl Polymer to a topical composition the contains three otherUV absorbers (7.5% Homosalate, 5% Octisalate, and 3% Avobenzone)provides an SPF of about 15.6, and provides an increase in SPF of about4 to sunscreen compositions.

Example 10

Sunscreen compositions where prepared that included 2% of the polymerprepared in Example 3 (a polymer containing the monomers containingcrylene moieties (as shown in formulae (I) and (II) wherein R² and R⁶are 2,2-dimethylpropane, and R¹ and R⁵ are C₁₆ straight chain alkylgroups) and monomers that contain C₁₆ fatty esters (as shown in formulae(III) and (IV) wherein R⁹ and R¹¹ are C₁₆ straight chain alkyl groups,and R¹⁰ and R¹² are C₂₂ straight chain alkyl groups), which shall bereferred to throughout the examples as “Crylene/Behenyl Polymer,” andthat substituted the Crylene/Behenyl Polymer with the non-UV absorbingOctyldodecanol using the ingredients listed in Table VIII below:

TABLE VIII Sunscreen w/0% Sunscreen w/2% Phase Ingredient Polymer (wt.%) Polymer (wt. %) A Octyl salicylate  5.00%  5.00% Homosalate  7.50% 7.50% Diethylhexyl 2,6-  2.50%  2.50% naphthalate Dimethyl capramide 1.00%  1.00% Diethylhexyl malate  4.51%  4.51% Dimethicone  0.4%  0.4%B Avobenzone  3.00%  3.00% Benzophenone-3  0.49%  0.49% C PVP/EicoseneCopolymer  2.00% Crylene/Behenyl Polymer  2.00% D Steric Acid  3.2% 3.2% Sorbitan isostearate  3.8%  3.8% Polyglyceryl-3 methyl  3.00% 3.00% glucose distearate Methylpropanediol  2.0%  2.0% E Water 55.87%55.87% Disodium EDTA  0.05%  0.05% Carbomer  0.05%  0.05% Glycerin    3%   3% Phenoxyethanol,  0.60%  0.60% Methylparaben, Ethylparaben,Propylparaben, and Isobutylparaben Triethanolamine  1.78%  1.78% FSilica  0.25%  0.25%

Oil-in-water emulsions were created, wherein the aqueous phase includeda mixture of the ingredients in Phase E, and the oil phase included amixture of the ingredients of Phases A, B, C, and D. The emulsions wereprepared by combining the ingredients of Phase A, and adding thismixture of ingredients to a vessel, and heating the vessel to about 90°C. The ingredients from Phases B, C, and D were then added to the heatedvessel with stirring until the mixture became clear and homogeneous. Inanother vessel, the water, Disodium EDTA, and Carbomer were added to thevessel, and the vessel was stirred and heated to 80° C. Just beforecombining the aqueous and oil phases, the remaining ingredients fromPhase E were added to vessel containing the aqueous mixture and thesilica was added to the stirring mixture of the oil phase. Withhomogenization, the oil phase (contents from Phases A-D, and F in TableVIII) at 86° C. was added to the vessel containing the aqueous phase,which was at 84° C. The resulting mixture was homogenized for threeminutes, and then the vessel was remove from heat source and allowed tocool. The mixture was stirred until a smooth cream was formed. Theresulting creams were packaged to avoid the inadvertent photodegradationof the UV-absorbing compounds, and the creams were then used to test thephotostability of the compositions.

The resulting sunscreens were tested for photostability by measuringabsorbance on a Labsphere UV-1000S Ultraviolet Transmittance Analyzer(software version 1.27) before and after irradiation with a Solar LightCompany model 16S solar simulator (equipped with a UG11 filter to blockradiation greater than 400 nm, WG320 filter that transmits UV-radiationgreater than 290 nm), and a removable WG335 filter that transmitsUV-radiation greater than 320 nm). Output was monitored by a PMA 2105UV-B DCS Detector (biologically weighted) or a PMA 2114 UV-A Detectorand controlled by a PMA 2100 Automatic Dose Controller (available fromSolar Light Co.).

To test stability, a synthetic skin substrate was used for testing thesunscreen compositions (VITRO-SKIN substrate (Lot No. 3059) by IMS, Inc.of Milford, Conn.). To prepare the substrate, a 300 g solution of 18 wt.% glycerin and 82 wt. % deionized water was added to a hydrating chamber(IMS), and a sheet of VITRO-SKIN was placed in the hydrating chamber andleft overnight (approx. 16 hours). Several 6.5 cm squares were cut fromthe hydrated VITRO-SKIN and used for absorbance measurements.

To prepare slides for testing, a minimum 100 μl of sunscreen compositionis drawn or placed into a pipet tip (Justor 1100DG, set to dispense 100μl). Using steady, even pressure on the pipette plunger, the testsubstance was applied to VITRO-SKIN square in a pattern of at least 50small dots arranged to cover a 6 cm center of a square. The VITRO-SKINsquare was then placed on a foam block, and the test material was spreadby finger (covered with a latex glove or finger cot), first in acircular motion, then by a side-to-side motion during which theVITRO-SKIN is deformed by the pressure. The square was then mounted in aslide holder (60 mm×60 mm glassless slide mounts with metal masks byGepe Management AG, Zug, Switzerland) and allowed to dry for 30-60minutes.

It has been found that to avoid certain errors of an as yet unknowncause, it is advantageous to pre-expose the tested spot on the slide to2 MED, and then zero the detector to treat the pre-exposed spot as a 0MED reading. Thus, using the PMA 2105 UV-B detector, a pre-exposure of 2MED was made. Immediately following the pre-exposure, the slide is takento the UV Transmittance Analyzer and the irradiated spot is scanned. Theoriginal scan is deleted, and the new scan is saved as the baseline (“0MED”) scan.

To test stability of a slide in the UV-B range, the PMA 2105 was used,and the slide was positioned on the UV transmittance analyzer usingregistration marks, and a scan of a 1 cm spot on the slide wasperformed. The slide was then transferred to a holder placed adjacent tothe solar simulator and, using a calipers, was positioned such that thebeam of UV radiation exiting the solar simulator illuminated the same 1cm spot on the slide. To test stability of a slide in the UV-A range,the PMA 2114 was substituted for the PMA 2105, and a WG335 filter wasinstalled in the beam path. The following software settings were used:UV-B=290-320 nm; UV-A=320-400 nm. Following an exposure of 5 MED, theslide was again placed in position on the UV transmittance analyzer, anda scan of the exposed spot was performed. The procedure was repeated onthe same 1 cm spot on the slide until the desired total radiation dosagewas achieved (approximately 35 MED for the UV-B studies, and 120 J/cm²for the UV-A studies).

FIG. 12 is a graph of the absorbance of the sunscreen compositionslisted in Table VIII. As shown in FIG. 12, the sunscreen compositionthat does includes 2% of the Crylene/Behenyl Polymer achieves thehighest absorbance as compared to the sunscreen composition of TableVIII that does not include the polymer.

Example 11

A determination of the Sun Protection Factor (SPF) of the sunscreencompositions that were prepared in Example 8 was performed. To test theSPF of the compositions, each slide was placed on the UV transmittanceanalyzer and scans were taken from five locations on the slide. An SPFreport was generated for each slide using the Labsphere softwareUV1000S, Version 1.27.

The results of the SPF testing for the composition listed in Table VIIIare shown below in Table IX:

TABLE IX Composition SPF Results Sunscreen Composition Scan No. 1 18.14with 0% Polymer Scan No. 2 20.21 (Table VIII) Scan No. 3 20.10 Scan No.4 21.65 Scan No. 5 23.80 Average SPF 20.8 Sunscreen Composition Scan No.1 23.40 with 2% Polymer Scan No. 2 24.33 (Table VIII) Scan No. 3 25.13Scan No. 4 22.72 Scan No. 5 23.22 Average SPF 23.8

The results shown in Table IX indicate that the addition of 2%Crylene/Behenyl Polymer to a topical composition provides an increase inSPF of about 3 to sunscreen compositions.

Example 12

The water resistance of sunscreen compositions listed in Table VIII wastested by immersing slides of VITRO-SKIN, which contain thecompositions, in moving water for a period of time and testing theslides for a loss in absorbance as measured by SPF. The slides weretested before and after being immersed in water and the results werecompared.

The slides were prepared according to the procedure set forth in Example10, and each slide was placed in a beaker and the top, bottom, and sidesof the slides were secured in the beaker with binder clips. The slideswere then completely immersed in water by the addition of two liters oftap water to the beaker. The beaker was placed on a stir table and astir bar is placed on the bottom of the beaker. The stir bar is set inmotion to circulate the water with a mild vortex. After 40 minutes, theslides were removed from the beaker, shaken to remove excess water, andallowed to air-dry for 30 minutes. Scans are taken from five locationson the slides. The absorbance spectra and an SPF report was generatedfor each composition.

The results of the SPF reports are summarized in Table X below:

TABLE X Pre-Immersion Post-Immersion Composition SPF Results SPF ResultsSunscreen Composition 23.58 12.10 with 0% Polymer (Table VIII) SunscreenComposition 23.19 20.69 with 2% Polymer (Table VIII)

As shown in Table X, the immersion of the sunscreen compositioncontaining 0% of the Crylene/Behenyl Polymer in water causes asignificant loss of SPF. In contrast, when the sunscreen compositionlisted in Table VIII that included 2% Crylene/Behenyl Polymer wasimmersed in water, there was only a slight decrease in the SPF resultsas compared to the pre-immersion SPF results. However, this test and theothers referenced in the accompanying demonstrate the polymer's abilityto: (a) provide water resistance (i.e., water proofing) to thecomposition, and thereby avoiding loss of the composition uponimmersion; (2) absorb UV-radiation; and (3) stabilize the otherphotoactive compounds in the composition by, for example, absorbing theexcited state energy of other photoactive compounds and rapidlydissipating that energy.

FIG. 13 is a graph of the absorbance of the sunscreen composition listedin Table VI that included 2% Crylene/Behenyl Polymer in the composition.As shown in FIG. 13, the absorbance spectra indicates that the immersionof the composition with 2% Crylene/Behenyl Polymer in moving water for40 minutes causes less of a loss in the absorbance over the entireUV-spectra (290-400 nm) than the composition that does not include theCrylene/Behenyl Polymer.

The foregoing description is given for clearness of understanding only,and no unnecessary limitations should be understood therefrom, asmodifications within the scope of the compounds, compositions, andmethods described herein may be apparent to those having ordinary skillin the art.

1. A polymer comprising monomers selected from the group consisting of amonomer of formula (I), a monomer of formula (II), and combinationsthereof:

wherein R¹ and R⁵ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R² and R⁶ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne, aryl,substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryland substituted heterocycloalkyl; R³, R⁴, R⁷ and R⁸ are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether,C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,substituted heteroaryl, substituted heterocycloalkyl, hydroxyl, ester,carboxy, cyano, amino, amido, sulfur and halo; b, c, e and f are each inthe range of 0 to 4; a and d are each in the range of 0 to 200, and thesum of a and d is at least
 1. 2. The polymer of claim 1, furthercomprising monomers selected from the group consisting of a monomer offormula (III), a monomer of formula (IV), a monomer of formula (V), amonomer of formula (VI), and combinations thereof:

wherein R⁹, R¹¹, R¹³ and R¹⁴ are the same or different and are selectedfrom the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substitutedpolyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substituted cycloalkyl,C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne; R¹⁰ and R¹² arethe same or different and are selected from the group consisting ofC₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne; and g, h, i and j are each in the range of 0 to
 200. 3. Thepolymer of claim 2, wherein R¹⁰ and R¹² are the same or different andare selected from the group consisting of C₁₀-C₃₅ alkyl groups.
 4. Thepolymer of claim 3, wherein R¹⁰ and R¹² are the same or different andare selected from the group consisting of C₁₆, C₁₈, and C₂₂ alkylgroups.
 5. The polymer of claim 2, wherein R¹⁰ and R¹² are the same ordifferent and are selected from the group consisting of C₃-C₃₀ polyethergroups.
 6. The polymer of claim 5, wherein R¹⁰ and R¹² are the same andare 2-butoxy-1-ethoxyethane.
 7. The polymer of claim 1, wherein R² andR⁶ are the same or different and are selected from the group consistingof C₂-C₁₅ alkyl groups.
 8. The polymer of claim 7, wherein R² and R⁶ arethe same and are 2,2-dimethylpropane.
 9. The polymer of claim 2, whereinthe sum of g and h is at least
 1. 10. The polymer of claim 2, whereinR¹, R⁵, R⁹, R¹¹, R¹³ and R¹⁴ are the same or different and are selectedfrom the group consisting of C₅-C₂₅ alkyl groups.
 11. The polymer ofclaim 10, wherein R¹, R⁵, R⁹, R¹¹, R¹³ and R¹⁴ are the same and are C₁₆straight chain alkyl groups.
 12. The polymer of claim 1, wherein theWeight-Average Molecular Weight of said polymer is in the range of about30,000 to about 110,000.
 13. A sunscreen composition, comprising amixture of a photoactive compound, and a polymer comprising monomersselected from the group consisting of a monomer of formula (I), amonomer of formula (II), and combinations thereof:

wherein R¹ and R⁵ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R² and R⁶ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne, aryl,substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryland substituted heterocycloalkyl; R³, R⁴, R⁷ and R⁸ are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether,C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,substituted heteroaryl, substituted heterocycloalkyl, hydroxyl, ester,carboxy, cyano, amino, amido, sulfur and halo; b, c, e and f are each inthe range of 0 to 4; a and d are each in the range of 0 to 200, and thesum of a and d is at least
 1. 14. The composition of claim 13, whereinsaid polymer further comprises monomers selected from the groupconsisting of a monomer of formula (III), a monomer of formula (IV), amonomer of formula (V), a monomer of formula (VI), and combinationsthereof:

wherein R⁹, R¹¹, R¹³ and R¹⁴ are the same or different and are selectedfrom the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substitutedpolyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substituted cycloalkyl,C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne; R¹⁰ and R¹² arethe same or different and are selected from the group consisting ofC₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne; and g, h, i and j are each in the range of 0 to
 200. 15. Thecomposition of claim 14, wherein R¹⁰ and R¹² are the same or differentand are selected from the group consisting of C₁₀-C₃₅ alkyl groups. 16.The composition of claim 15, wherein R¹⁰ and R¹² are the same ordifferent and are selected from the group consisting of C₁₆, C₁₈, andC₂₂ alkyl groups.
 17. The composition of claim 14, wherein R¹⁰ and R¹²are the same or different and are selected from the group consisting ofC₃-C₃₀ polyether groups.
 18. The composition of claim 17, wherein R¹⁰and R¹² are the same and are 2-butoxy-1-ethoxyethane.
 19. Thecomposition of claim 13, wherein R² and R⁶ are the same or different andare selected from the group consisting of C₂-C₁₅ alkyl groups.
 20. Thecomposition of claim 19, wherein R² and R⁶ are the same and are2,2-dimethylpropane.
 21. The composition of claim 13, wherein saidpolymer is present said composition in an amount in the range of about0.01% to about 30% by weight of the total weight of the composition. 22.The composition of claim 21, wherein said polymer is present saidcomposition in an amount in the range of about 0.01% to about 10% byweight of the total weight of the composition.
 23. The composition ofclaim 13, further comprising a diester or polyester of naphthalenedicarboxylic acid selected from the group consisting of compounds offormulae (XXX) and (XXXI), and combinations thereof:

wherein R⁹³ and R⁹⁴ are the same or different and selected from thegroup consisting of C₁-C₂₂ alkyl groups, diols having the structureHO—R⁹¹—OH and polyglycols having the structure HO—R⁹⁰—(—O—R⁹¹—)_(γ)—OH;wherein each R⁹⁰ and R⁹¹ is the same or different and selected from thegroup consisting of C₁-C₆ straight or branched chain alkyl groups; andwherein α and γ are each in a range of 1 to 100 and β is in a range of 0to
 100. 24. A method of protecting human skin from ultraviolet radiationcomprising topically applying to said skin, in a cosmetically acceptablecarrier, the composition of claim
 13. 25. A method of protecting asurface from ultraviolet radiation, comprising topically applying tosaid surface, in a cosmetically acceptable carrier, a polymer comprisingmonomers selected from the group consisting of a monomer of formula (I),a monomer of formula (II), and combinations thereof:

wherein R¹ and R⁵ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R² and R⁶ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne, aryl,substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryland substituted heterocycloalkyl; R³, R⁴, R⁷ and R⁸ are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether,C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,substituted heteroaryl, substituted heterocycloalkyl, hydroxyl, ester,carboxy, cyano, amino, amido, sulfur and halo; b, c, e and f are each inthe range of 0 to 4; a and d are each in the range of 0 to 200, and thesum of a and d is at least
 1. 26. The method of claim 25, wherein saidpolymer further comprises monomers selected from the group consisting ofa monomer of formula (III), a monomer of formula (IV), a monomer offormula (V), a monomer of formula (VI), and combinations thereof:

wherein R⁹, R¹¹, R¹³ and R¹⁴ are the same or different and are selectedfrom the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substitutedpolyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substituted cycloalkyl,C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne; R¹⁰ and R¹² arethe same or different and are selected from the group consisting ofC₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne; and g, h, i and j are each in the range of 0 to
 200. 27. Themethod of claim 26, wherein R¹⁰ and R¹² are the same or different andare selected from the group consisting of C₁₀-C₃₅ alkyl groups.
 28. Themethod of claim 27, wherein R¹⁰ and R¹² are the same or different andare selected from the group consisting of C₁₆, C₁₈, and C₂₂ alkylgroups.
 29. The method of claim 26, wherein R¹⁰ and R¹² are the same ordifferent and are selected from the group consisting of C₃-C₃₀ polyethergroups.
 30. The method of claim 29, wherein R¹⁰ and R¹² are the same andare 2-butoxy-1-ethoxyethane.
 31. The method of claim 25, wherein R² andR⁶ are the same or different and are selected from the group consistingof C₂-C₁₅ alkyl groups.
 32. The method of claim 31, wherein R² and R⁶are the same and are 2,2-dimethylpropane.
 33. The method of claim 26,wherein the sum of g and h is at least
 1. 34. The method of claim 25,wherein said surface comprises human skin.
 35. A method of waterproofinga surface, comprising applying a polymer comprising monomers selectedfrom the group consisting of a monomer of formula (I), a monomer offormula (II), and combinations thereof to a selected area of saidsurface:

wherein R¹ and R⁵ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R² and R⁶ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne, aryl,substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryland substituted heterocycloalkyl; R³, R⁴, R⁷ and R⁸ are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether,C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,substituted heteroaryl, substituted heterocycloalkyl, hydroxyl, ester,carboxy, cyano, amino, amido, sulfur and halo; b, c, e and f are each inthe range of 0 to 4; a and d are each in the range of 0 to 200, and thesum of a and d is at least
 1. 36. The method of claim 35, wherein saidpolymer further comprises monomers selected from the group consisting ofa monomer of formula (III), a monomer of formula (IV), a monomer offormula (V), a monomer of formula (VI), and combinations thereof:

wherein R⁹, R¹¹, R¹³ and R¹⁴ are the same or different and are selectedfrom the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substitutedpolyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substituted cycloalkyl,C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne; R¹⁰ and R¹² arethe same or different and are selected from the group consisting ofC₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne; and g, h, i and j are each in the range of 0 to
 200. 37. Themethod of claim 36, wherein R¹⁰ and R¹² are the same or different andare selected from the group consisting of C₁₀-C₃₅ alkyl groups.
 38. Themethod of claim 37, wherein R¹⁰ and R¹² are the same or different andare selected from the group consisting of C₁₆, C₁₈, and C₂₂ alkylgroups.
 39. The method of claim 36, wherein R¹⁰ and R¹² are the same ordifferent and are selected from the group consisting of C₃-C₃₀ polyethergroups.
 40. The method of claim 39, wherein R¹⁰ and R¹² are the same andare 2-butoxy-1-ethoxyethane.
 41. The method of claim 35, wherein R² andR⁶ are the same or different and are selected from the group consistingof C₂-C₁₅ alkyl groups.
 42. The method of claim 41, wherein R² and R⁶are the same and are 2,2-dimethylpropane.
 43. The method of claim 36,wherein the sum of g and h is at least
 1. 44. The method of claim 35,wherein said surface comprises human skin.
 45. A method for forming afilm over at least part of a surface, comprising spreading a polymercomprising monomers selected from the group consisting of a monomer offormula (I), a monomer of formula (II), and combinations thereof on saidpart of said surface:

wherein R¹ and R⁵ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R² and R⁶ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne, aryl,substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryland substituted heterocycloalkyl; R³, R⁴, R⁷ and R⁸ are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether,C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,substituted heteroaryl, substituted heterocycloalkyl, hydroxyl, ester,carboxy, cyano, amino, amido, sulfur and halo; b, c, e and f are each inthe range of 0 to 4; a and d are each in the range of 0 to 200, and thesum of a and d is at least
 1. 46. The method of claim 45, wherein saidpolymer further comprises monomers selected from the group consisting ofa monomer of formula (III), a monomer of formula (IV), a monomer offormula (V), a monomer of formula (VI), and combinations thereof:

wherein R⁹, R¹¹, R¹³ and R¹⁴ are the same or different and are selectedfrom the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substitutedpolyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substituted cycloalkyl,C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne; R¹⁰ and R¹² arethe same or different and are selected from the group consisting ofC₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne; and g, h, i and j are each in the range of 0 to
 200. 47. Themethod of claim 46, wherein R¹¹ and R¹² are the same or different andare selected from the group consisting of C₁₀-C₃₅ alkyl groups.
 48. Themethod of claim 47, wherein R¹⁰ and R¹² are the same or different andare selected from the group consisting of C₁₆, C₁₈, and C₂₂ alkylgroups.
 49. The method of claim 46, wherein R¹⁰ and R¹² are the same ordifferent and are selected from the group consisting of C₃-C₃₀ polyethergroups.
 50. The method of claim 49, wherein R¹⁰ and R¹² are the same andare 2-butoxy-1-ethoxyethane.
 51. The method of claim 45, wherein R² andR⁶ are the same or different and are selected from the group consistingof C₂-C₁₅ alkyl groups.
 52. The method of claim 51, wherein R² and R⁶are the same and are 2,2-dimethylpropane.
 53. The method of claim 46,wherein the sum of g and h is at least
 1. 54. The method of claim 45,wherein said surface comprises human skin.
 55. A method ofphotostabilizing a dibenzoylmethane derivative, said method comprisingthe step of, adding to said dibenzoylmethane derivative aphotostabilizing amount of a polymer comprising monomers selected fromthe group consisting of a monomer of formula (I), a monomer of formula(II), and combinations thereof:

wherein R¹ and R⁵ are the same or different and are selected from thegroup consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkyne; R² and R⁶ are the same or differentand are selected from the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne, aryl,substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryland substituted heterocycloalkyl; R³, R⁴, R⁷ and R⁸ are the same ordifferent and are selected from the group consisting of C₁-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether,C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,substituted heteroaryl, substituted heterocycloalkyl, hydroxyl, ester,carboxy, cyano, amino, amido, sulfur and halo; b, c, e and f are each inthe range of 0 to 4; a and d are each in the range of 0 to 200, and thesum of a and d is at least
 1. 56. The method of claim 55, wherein saidpolymer further comprises monomers selected from the group consisting ofa monomer of formula (III), a monomer of formula (IV), a monomer offormula (V), a monomer of formula (VI), and combinations thereof:

wherein R⁹, R¹¹, R¹³ and R¹⁴ are the same or different and are selectedfrom the group consisting of C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀ polyether, C₁-C₅₀ substitutedpolyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substituted cycloalkyl,C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkyne; R¹⁰ and R¹² arethe same or different and are selected from the group consisting ofC₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₅₀polyether, C₁-C₅₀ substituted polyether, C₁-C₅₀ substituted alkyl, C₃-C₈substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substitutedalkyne; and g, h, i and j are each in the range of 0 to
 200. 57. Themethod of claim 56, wherein R¹⁰ and R¹² are the same or different andare selected from the group consisting of C₁₀-C₃₅ alkyl groups.
 58. Themethod of claim 57, wherein R¹⁰ and R¹² are the same or different andare selected from the group consisting of C₁₆, C₁₈, and C₂₂ alkylgroups.
 59. The method of claim 56, wherein R¹⁰ and R¹² are the same ordifferent and are selected from the group consisting of C₃-C₃₀ polyethergroups.
 60. The method of claim 59, wherein R¹⁰ and R¹² are the same andare 2-butoxy-1-ethoxyethane.
 61. The method of claim 55, wherein R² andR⁶ are the same or different and are selected from the group consistingof C₂-C₁₅ alkyl groups.
 62. The method of claim 61, wherein R² and R⁶are the same and are 2,2-dimethylpropane.
 63. The method of claim 56,wherein the sum of g and h is at least 1.